Chemical compounds

ABSTRACT

The use of a compound of formula I 
                         
wherein
     X is (i), (ii) or (iii)   

     
       
         
         
             
             
         
       
         
         Y is O, S(O) m , NR 3 , CR 5 R 6 , CR 5 R 6 —CR 7 R 8 , O—CR 7 R 8 , S(O) m —CR 7 R 8 , NR 3 —CR 7 R 8 , CR 5 R 6 —O, CR 5 R 6 —S(O) m , CR 5 R 6 —NR 3 , SO 2 —NR 3 , NR 3 —SO 2 , NR 3 —O or O—NR 3 ; 
         m is 0, 1, or 2; 
         the ring (T) 
       
    
                         
is a 5- or 6-membered aromatic or heteroaromatic ring; R 1  to R 10  are specified organic groups and n and is 0, 1, 2, 3 or 4; or salts or N-oxides thereof or compositions containing them in controlling insects, acarines, nematodes or molluscs. Novel compounds are also provided.

This application is a divisional application of U.S. Ser. No. 12/063,869, filed Jun. 16, 2008, which is a 371 of International Application No. PCT/GB2006/002886 filed Aug. 2, 2006, which claims priority to GB 0516706.9 filed Aug. 15, 2005, the contents of which are incorporated herein by reference.

The present invention relates to thiazoline derivatives, to processes for preparing them, to insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.

Thiazoline derivatives with pharmaceutical properties are disclosed in for example in U.S. Pat. No. 3,636,219, IN 179230 and Coll. Czech Chem. Comm, 1992, 57, 415.

It has now surprisingly been found that certain thiazolines have good insecticidal properties.

The present invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I):

wherein X is (i), (ii) or (iii)

Y is O, S(O)_(m), NR³, CR⁵R⁶, CR⁵R⁶—CR⁷R⁸, O—CR⁷R⁸, S(O)_(m)—CR⁷R⁸, NR³—CR⁷R⁸, CR⁵R⁶—O, CR⁵R⁶—S(O)_(m), CR⁵R⁶—NR³, SO₂—NR³, NR³—SO₂, NR³—O or O—NR³; m is 0, 1, or 2; the ring (T)

is a 5- or 6-membered aromatic or heteroaromatic ring; R¹, R², R⁵, R⁶, R⁷ and R⁸ are each independently H, OH, halogen, nitro, cyano, rhodano, carboxy, formyl, formyloxy, G-, G-O—, G-S—, G-A-, R²¹R²²N—, R²¹R²²N-A-, G-O-A-, G-S-A-, G-A-O—, G-A-S—, G-A-NR²³—, R²¹R²²N-A-O—, R²¹R²²N-A-S—, R²¹R²²N-A-NR²³—, G-O-A-O—, G-O-A-S—, G-O-A-NR²³—, G-S-A-O, G-S-A-NR²³—, or R²⁰S(O)(═NR¹⁷)—; or two of the groups R¹, R², R⁵, R⁶, R⁷ and R⁸ attached to the same carbon atom are ═O, ═S, ═NR¹¹ or ═CR¹²R¹³, or the groups R¹ and R², R⁵ and R⁶ or R⁷ and R⁸ together with the carbon atom to which they are attached form a three to six membered ring, containing at least 2 carbon atoms and optionally containing one or two sulfur and/or one or two non-adjacent oxygen atoms or a group NR¹⁴, the ring being optionally substituted by C₁-C₆ alkyl; or two of the groups R¹, R², R⁵, R⁶, R⁷ and R⁸ attached to different atoms together with the atoms they are attached form a three to seven membered ring, that optionally contains one or two sulfur and/or one or two non-adjacent oxygen atoms or a group NR¹⁴, the ring being optionally substituted by C₁-C₆ alkyl or two of the groups R¹, R², R⁵, R⁶, R⁷ and R⁸ attached to adjacent atoms combine to form a bond; R¹⁰ is H, OH, cyano, formyl, tri(C₁-C₆ alkyl)silyl, G-, G-O—, G-S—, G-S—S—, G-A-, R²⁴R²⁵N—, R²⁴R²⁵N—S—, R²⁴R²⁵N-A-, R¹⁸N═C(R¹⁹)—, G-A-NR⁶⁹—, R⁷⁰R⁷¹C═N—, G-O-A- or G-S-A-, R¹¹ is H, OH, nitro, cyano, formyl, formyloxy, G-, G-O—, G-A-, R³⁶R³⁷N—, G-C(O)—O—, G-C(O)—NR²⁶—, R³⁶R³⁷N—C(O)O—, G—OC(O)O—, G-OC(O)—NR²⁶—; R¹² and R¹³ are each independently H, halogen, nitro, cyano, formyl, formyloxy, G-, G-O—, G-S—, G-A-, R⁴⁰R⁴¹N—, R⁴⁰R⁴¹N-A-, G-O-A-, G-A-O—, R⁴⁰R⁴¹N-A-O—, R⁴⁰R⁴¹N-A-S—, G-O-A-O—, G-O-A-S—, G-O-A-NR³⁰—, or R¹² and R¹³ together with the carbon atom to which they are attached form a 3 to 6 membered carbocyclic ring; R³, R¹⁴, R¹⁵ and R¹⁶ are each independently H, OH, cyano, formyl, G-, G-O—, G-S—, G-A-, R²⁷R²⁸N—, R²⁷R²⁸N-A-, G-O-A-, G-S-A-, G-A-NR²⁹—, R²⁷R²⁸NA-NR²⁹—, G-O-A-NR²⁹— or G-S-A-NR²⁹—; each R⁴ is independently OH, halogen, nitro, cyano, azido, rhodano, isothiocyanato, carboxy, formyl, formyloxy, G-, G-O—, G-S—, G-A-, R³¹R³²N—, R³¹R³²N-A-, G-O-A-, G-S-A-, G-A-O—, G-A-S—, G-A-NR³³—, R³¹R³²N-A-O—, R³¹R³²N-A-S—, R³¹R³²N-A-NR³³—, G-O-A-O—, G-O-A-S—, S—, G-O-A-NR³³—, G-S-A-O, G-S-A-NR³³—, R²⁰S(O)(═NR¹⁷)—, R¹⁸N═C(R¹⁹)—, R⁴⁴R⁴⁵P(O)— or R⁴⁴R⁴⁵P(S)—, or 2 adjacent groups R⁴ together with the carbon atoms to which they are attached form a 4, 5, 6, or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen, or a group R⁴ together with a group R³, R⁵ or R⁹ and the atoms to which they are attached form a 5-7 membered ring optionally containing an NR¹⁵ group or an S or O atom, the ring being optionally substituted by C₁-C₆ alkyl; n is 0, 1, 2, 3 or 4; R⁹ is H, formyl, G, G-A-, R³⁴R³⁵N-A-, G-O-A- or G-S-A-, or R⁹ together with a group R¹, R⁵ or R⁷ and the atoms to which they are attached may form a three to seven membered ring, that optionally may contain one or two sulfur and/or one or two non-adjacent oxygen atoms or a group NR¹⁶; R¹⁷ is H, G-, G-C(O)—, or G-OC(O)—; R¹⁸ is H, OH, cyano, nitro, G-, G-O— or R³⁸R³⁹N—; R¹⁹ is H, cyano, G-, G-O—, G-S— or R⁴²R⁴³N—; R²⁰ is C₁₋₆ alkyl, optionally substituted phenyl, optionally substituted benzyl; each of the groups R²¹ to R⁴³ inclusive are independently H or G-, or two R²¹, R²², R²⁷, R²⁸, R³¹, R³², R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴², R⁴³ groups, together with the N atom to which they are attached, form a group N═CR^(a)R^(b) (where R^(a) and R^(b) are H, or C₁₋₆ alkyl) or two R²¹, R²², R²⁴, R²⁵, R²⁷, R²⁸, R³¹, R³², R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴², R⁴³ groups, together with the N atom to which they are attached, form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one to four C₁₋₆ alkyl groups; R⁴⁴ and R⁴⁵ are independently C₁₋₆alkyl, C₁₋₆-alkoxy, phenyl, phenoxy; G is optionally substituted C₁₋₁₂ alkyl, optionally substituted C₂₋₁₂ alkenyl, optionally substituted C₂₋₁₂ alkynyl, optionally substituted C₃₋₈ cycloalkyl, optionally substituted C₃₋₈ cycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl; R⁶⁹ is H, G-, G-C(O)—, or G-OC(O)—; R⁷⁰ and R⁷¹ are independently H, cyano, nitro, G-, G-O—, G-S—, or R⁷⁰ and R⁷¹ together with the carbon atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one to four C₁₋₆ alkyl groups; A is S(O), SO₂, C(O) or C(S); or salts or N-oxides thereof.

The compounds of formula (I) may exist in different geometric or optical isomers or different tautomeric forms. One or more centres of chirality may be present, for example on the chiral carbon atoms CR¹R², CR⁵R⁶, CR⁷R⁸, CR⁹, or a chiral carbon unit in the group G, or a chiral —S(O)— unit, in which case compounds of the formula (I) may be present as pure enantiomers, mixtures of enantiomers, pure diastereomers or mixtures of diastereomers. There may be double bonds present in the molecule, such as C═C or C═N bonds, in which case compounds of formula (I) may exist as single isomers of mixtures of isomers. Centres of tautomerisation may be present. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.

The compounds of formula (I) contain an amidine moiety, which can exist in two tautomeric forms when R¹⁰ is hydrogen. One of these forms contains an exocyclic C═N double bond, and one of them contains an endocyclic C═N double bond. When the C═N double bond is exocyclic this double bond can exist in two geometric forms E and Z as shown by formula (I′) and (I″). Each form can be latentiated with a group R¹⁰. This group R¹⁰ is selected to allow its removal by one or a combination of biochemical, chemical or physical processes to afford compounds of formula I where R¹⁰ is H before, during or following application to the treated area or plants. Examples of these processes include enzymatic cleavage, chemical hydrolysis and photolysis. Compounds bearing groups R¹⁰ may offer certain advantages, such as improved penetration of the cuticula of the plants treated, increased tolerance of crops, improved compatibility or stability in formulated mixtures containing other herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides, increased movement in soils or reduced leaching in soils.

Suitable acid addition salts include those with an inorganic acid such as hydrochloric, hydrobromic, sulfuric, nitric and phosphoric acids, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic and phthalic acids, or sulphonic acids such as methane, benzene and toluene sulphonic acids. Other examples of organic carboxylic acids include haloacids such as trifluoroacetic acid.

N-oxides are oxidised forms of tertiary amines or oxidised forms of nitrogen containing heteroaromatic compounds. They are described in many books for example in “Heterocyclic N-oxides” by Angelo Albini and Silvio Pietra, CRC Press, Boca Raton, Fla., 1991.

Each alkyl moiety either alone or as part of a larger group (such as G, or alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or neo-pentyl. The alkyl groups are suitably C₁ to C₁₂ alkyl groups, but are preferably C₁-C₁₀, more preferably C₁-C₈, even more preferably C₁-C₆ and most preferably C₁-C₄ alkyl groups.

The ring or chain forming alkylene, alkenylene and alkinylene groups can optionally be further substituted by one or more halogen, C₁-C₃ alkyl, and/or C₁-C₃ alkoxy groups.

When present, the optional substituents on an alkyl moiety (alone or as part of a larger group such as alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) include one or more of halogen, nitro, cyano, rhodano, isothiocyanato, C₃₋₇ cycloalkyl (itself optionally substituted with C₁₋₆ alkyl or halogen), C₅₋₇ cycloalkenyl (itself optionally substituted with C₁₋₆ alkyl or halogen), hydroxy, C₁₋₁₀ alkoxy, C₁₋₁₀ alkoxy(C₁₋₁₀)alkoxy, tri(C₁₋₄)alkylsilyl(C₁₋₆)alkoxy, C₁₋₆ alkoxycarbonyl(C₁₋₁₀)alkoxy, C₁₋₁₀ haloalkoxy, aryl(C₁₋₄)-alkoxy (where the aryl group is optionally substituted), C₃₋₇ cycloalkyloxy (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), C₂₋₁₀ alkenyloxy, C₂₋₁₀ alkynyloxy, SH, C₁₋₁₀ alkylthio, C₁₋₁₀ haloalkylthio, aryl(C₁₋₄)alkylthio (where the aryl group is optionally substituted), C₃₋₇ cycloalkylthio (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), tri(C₁₋₄)alkylsilyl(C₁₋₆)alkylthio, arylthio (where the aryl group is optionally substituted), C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, arylsulfonyl (where the aryl group may be optionally substituted), tri(C₁₋₄)alkylsilyl, aryldi(C₁₋₄)alkylsilyl, (C₁₋₄)alkyldiarylsilyl, triarylsilyl, formyl, C₁₋₁₀ alkylcarbonyl, HO₂C, C₁₋₁₀ alkoxycarbonyl, aminocarbonyl, C₁₋₆ alkylaminocarbonyl, di(C₁₋₆ alkyl)aminocarbonyl, N—(C₁₋₃ alkyl)-N—(C₁₋₃ alkoxy)aminocarbonyl, C₁₋₆ alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C₁₋₆)alkylaminocarbonyloxy, oximes and oximethers such as ═NOalkyl, ═NOhaloalkyl and ═NOaryl (itself optionally substituted), aryl (itself optionally substituted), heteroaryl (itself optionally substituted), heterocyclyl (itself optionally substituted with C₁₋₆ alkyl or halogen), aryloxy (where the aryl group is optionally substituted), heteroaryloxy, (where the heteroaryl group is optionally substituted), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C₁₋₆ alkyl or halogen), amino, C₁₋₆ alkylamino, di(C₁₋₆)alkylamino, C₁₋₆ alkylcarbonylamino, N—(C₁₋₆)alkylcarbonyl-N—(C₁₋₆)alkylamino, C₂₋₆ alkenylcarbonyl, C₂₋₆ alkynylcarbonyl, C₃₋₆ alkenyloxycarbonyl, C₃₋₆ alkynyloxycarbonyl, aryloxycarbonyl (where the aryl group is optionally substituted) and arylcarbonyl (where the aryl group is optionally substituted).

Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl, allyl and propargyl. Alkenyl and alkynyl moieties can contain one or more double and/or triple bonds in any combination. It is understood, that allenyl and alkylinylalkenyl are included in these terms.

When present, the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.

In the context of this specification acyl is optionally substituted C₁₋₆ alkylcarbonyl (for example acetyl), optionally substituted C₂₋₆ alkenylcarbonyl, optionally substituted C₃₋₆ cycloalkylcarbonyl (for example cyclopropylcarbonyl, optionally substituted C₂₋₆ alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF₃, CF₂Cl, CF₂H, CCl₂CH, FCH₂, ClCH₂, BrCH₂, CH₃CHF, CF₃CH₂ or CHF₂CH₂.

In the context of the present specification the terms “aryl”, “aromatic ring” and “aromatic ring system” refer to ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl. In addition, the terms “heteroaryl”, “heteroaromatic ring” or “heteroaromatic ring system” refer to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur. Examples of such groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2,1,3-benzoxadiazole, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl and indolizinyl. Preferred examples of heteroaromatic radicals include pyridyl, pyrimidyl, triazinyl, thienyl, furyl, oxazolyl, isoxazolyl, 2,1,3-benzoxadiazole and thiazolyl.

The terms heterocycle and heterocyclyl refer to a non-aromatic monocyclic or bicyclic ring system containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1,3-dioxolane, oxetane, tetrahydrofuran, morpholine, thiomorpholine and piperazine.

When present, the optional substituents on heterocyclyl include C₁₋₆ alkyl and C₁₋₆ haloalkyl as well as those optional substituents given above for an alkyl moiety.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Cycloalkenyl includes cyclopentenyl and cyclohexenyl.

When present, the optional substituents on cycloalkyl or cycloalkenyl include C₁₋₃ alkyl as well as those optional substituents given above for an alkyl moiety.

Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.

When present, the optional substituents on aryl or heteroaryl are selected independently, from halogen, nitro, cyano, rhodano, isothiocyanato, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy-(C₁₋₆)alkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₃₋₇ cycloalkyl (itself optionally substituted with C₁₋₆ alkyl or halogen), C₅₋₇ cycloalkenyl (itself optionally substituted with C₁₋₆ alkyl or halogen), hydroxy, C₁₋₁₀ alkoxy, C₁₋₁₀ alkoxy(C₁₋₁₀)alkoxy, tri(C₁₋₄)alkyl-silyl(C₁₋₆)alkoxy, C₁₋₆ alkoxycarbonyl(C₁₋₁₀)alkoxy, C₁₋₁₀ haloalkoxy, aryl(C₁₋₄)alkoxy (where the aryl group is optionally substituted with halogen or C₁₋₆ alkyl), C₃₋₇ cycloalkyloxy (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), C₂₋₁₀ alkenyloxy, C₂₋₁₀ alkynyloxy, SH, C₁₋₁₀ alkylthio, C₁₋₁₀ haloalkylthio, aryl(C₁₋₄)alkylthio C₃₋₇ cycloalkylthio (where the cycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen), tri(C₁₋₄)-alkylsilyl(C₁₋₆)alkylthio, arylthio, C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, arylsulfonyl, tri(C₁₋₄)alkylsilyl, aryldi(C₁₋₄)-alkylsilyl, (C₁₋₄)alkyldiarylsilyl, triarylsilyl, C₁₋₁₀ alkylcarbonyl, HO₂C, C₁₋₁₀ alkoxycarbonyl, aminocarbonyl, C₁₋₆ alkylaminocarbonyl, di(C₁₋₆ alkyl)-aminocarbonyl, N—(C₁₋₃ alkyl)-N—(C₁₋₃ alkoxy)aminocarbonyl, C₁₋₆ alkylcarbonyloxy, arylcarbonyloxy, di(C₁₋₆)alkylamino-carbonyloxy, aryl (itself optionally substituted with C₁₋₆ alkyl or halogen), heteroaryl (itself optionally substituted with C₁₋₆ alkyl or halogen), heterocyclyl (itself optionally substituted with C₁₋₆ alkyl or halogen), aryloxy (where the aryl group is optionally substituted with C₁₋₆ alkyl or halogen), heteroaryloxy (where the heteroaryl group is optionally substituted with C₁₋₆ alkyl or halogen), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C₁₋₆ alkyl or halogen), amino, C₁₋₆ alkylamino, di(C₁₋₆)alkylamino, C₁₋₆ alkylcarbonylamino, N—(C₁₋₆)alkylcarbonyl-N—(C₁₋₆)alkylamino, arylcarbonyl, (where the aryl group is itself optionally substituted with halogen or C₁₋₆ alkyl) or two adjacent positions on an aryl or heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen or C₁₋₆ alkyl. Further substituents for aryl or heteroaryl include aryl carbonyl amino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), (C₁₋₆)alkyloxycarbonylamino (C₁₋₆)alkyloxycarbonyl-N—(C₁₋₆)alkylamino, aryloxycarbonylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), aryloxycarbonyl-N—(C₁₋₆)alkylamino, (where the aryl group is substituted by C₁₋₆ alkyl or halogen), arylsulphonylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), arylsulphonyl-N—(C₁₋₆)alkylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), aryl-N—(C₁₋₆)alkylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), arylamino (where the aryl group is substituted by C₁₋₆ alkyl or halogen), heteroaryl amino (where the heteroaryl group is substituted by C₁₋₆ alkyl or halogen), heterocyclylamino (where the heterocyclyl group is substituted by C₁₋₆ alkyl or halogen), aminocarbonylamino, C₁₋₆ alkylaminocarbonyl amino, di(C₁₋₆)alkylaminocarbonyl amino, arylaminocarbonyl amino where the aryl group is substituted by C₁₋₆ alkyl or halogen), aryl-N—(C₁₋₆)alkylaminocarbonylamino where the aryl group is substituted by C₁₋₆ alkyl or halogen), C₁₋₆ alkylaminocarbonyl-N—(C₁₋₆)alkyl amino, di(C₁₋₆)alkylaminocarbonyl-N—(C₁₋₆)alkyl amino, arylaminocarbonyl-N—(C₁₋₆)alkyl amino where the aryl group is substituted by C₁₋₆ alkyl or halogen) and aryl-N—(C₁₋₆)alkylaminocarbonyl-N—(C₁₋₆)alkyl amino where the aryl group is substituted by C₁₋₆ alkyl or halogen).

For substituted phenyl moieties, heterocyclyl and heteroaryl groups it is preferred that one or more substituents are independently selected from halogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₃₋₇ cycloalkyl, nitro, cyano, CO₂H, C₁₋₆ alkylcarbonyl, C₁₋₆ alkoxycarbonyl, aryl, heteroaryl, R⁵⁰R⁵¹N or R⁵²R⁵³NC(O); wherein R⁵⁰, R⁵¹, R⁵² and R⁵³ are, independently, hydrogen or C₁₋₆ alkyl.

Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms.

It is to be understood that dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (C₁₋₆)alkyl groups. When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C₁₋₆) alkyl groups.

Preferably the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO₂C, C₁₋₁₀ alkoxy (itself optionally substituted by C₁₋₁₀ alkoxy), aryl(C₁₋₄)alkoxy, C₁₋₁₀ alkylthio, C₁₋₁₀ alkylcarbonyl, C₃₋₅ cycloalkylcarbonyl, C₁₋₁₀ alkoxycarbonyl, C₁₋₆ alkylaminocarbonyl, di(C₁₋₆ alkyl)aminocarbonyl, (C₁₋₆)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C₃₋₇ cycloalkyl (itself optionally substituted with (C₁₋₆)alkyl or halogen), C₃₋₇ cycloalkyloxy, C₅₋₇ cycloalkenyl, C₁₋₆ alkylsulfonyl, C₁₋₆ alkylsulfinyl, tri(C₁₋₄)alkylsilyl, tri(C₁₋₄)alkylsilyl(C₁₋₆)alkoxy, aryldi(C₁₋₄)alkylsilyl, (C₁₋₄)alkyldiarylsilyl and triarylsilyl.

Preferably the optional substituents on alkenyl or alkynyl include one or more of halogen, aryl and C₃₋₇ cycloalkyl.

A preferred optional substituent for heterocyclyl is C₁₋₃ alkyl.

Preferably the optional substituents for cycloalkyl include halogen, cyano and C₁₋₆ alkyl.

The optional substituents for cycloalkenyl preferably include C₁₋₃ alkyl, halogen and cyano.

Preferred groups for T, Y, R¹, R², R⁴, R⁹, and R¹⁰ in any combination thereof are set out below.

Y is preferably O, S, S(O), SO₂, NR³ or CR⁵R⁶ where R³, R⁵ and R⁶ are defined above. R³ is especially hydrogen, formyl, C₁₋₆ alkylcarbonyl, cyclopropylcarbonyl, C₁₋₆ alkoxycarbonyl, C₁₋₆ alkylsulfonyl, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₄ alkenyl, C₃₋₄ haloalkenyl, C₃₋₄ alkynyl or benzyl, or phenyl (where the phenyl containing groups are optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN or NO₂). Especially R⁵ and R⁶ are independently hydrogen, hydroxy, halogen, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, phenyl(C₁₋₃)alkyl (wherein the phenyl group may be optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino, dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C₃₋₅ cycloalkyl, 1,3-dioxolan-2-yl, phenyl (which may be optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino, dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkenyloxy, C₁₋₆ alkynyloxy, C₁₋₃ alkoxy(C₁₋₃)alkoxy, benzyloxy (where phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂), C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, NR⁵⁴R⁵⁵ (where R⁵⁴ and R⁵⁵ are independently hydrogen, C₁₋₆ alkyl or C₁₋₆ haloalkyl, C₁₋₄ alkoxy(C₁₋₄alkyl, formyl, C₂₋₆ alkylcarbonyl, phenylcarbonyl (where the phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂)), or R⁵ and R⁶ together with the carbon atom to which they are attached form a three to six membered ring, that optionally may contain one or two sulfur or one or two not adjacent oxygen atoms or a group NR⁵⁶ (where R⁵⁶ is hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₄ alkoxy(C₁₋₄alkyl, formyl, C₂₋₆ alkylcarbonyl), or when R⁵ together with R¹ forms a bond, or either R⁵ or R⁶ together with R¹ or R² and the carbon atom they are attached form a three to six membered ring, that optionally may contain one or two not adjacent oxygen atoms, or when R⁵ and R⁶ together form ═O, ═S, ═NR⁵⁷ or ═CR⁵⁸R⁵⁹, wherein R⁵⁷ is OH, optionally substituted C₁₋₆ alkoxy or C₁₋₄ alkylcarbonylamino, and R⁵⁸ and R⁵⁹ are independently H or C₁₋₆ alkyl.

More preferably Y is O or CR⁵R⁶ where R⁵ and R⁶ are hydrogen, hydroxy, fluoro, chloro, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkenyloxy, C₁₋₆ alkynyloxy, C₁₋₃ alkoxy(C₁₋₃)alkoxy or benzyloxy, or R⁵ and R⁶ together with the carbon atom to which they are attached form a three to six membered carbocyclic ring, or R⁵ and R¹ together form a bond, or R⁵ together with R¹ and the carbon atoms to which they are attached form a three to six membered carbocyclic ring.

Most preferably Y is CR⁵R⁶ where R⁵ and R⁶ are independently hydrogen or methyl, especially hydrogen.

Preferably each R¹ and R² group is independently hydrogen, hydroxy, halogen, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, phenyl(C₁₋₃)alkyl (wherein the phenyl group may be optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino, dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl), C₃₋₅ cycloalkyl, 1,3-dioxolan-2-yl, phenyl (which may be optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino, dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl), C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₂₋₆ alkenyloxy, C₂₋₆ alkinyloxy, C₁₋₃ alkoxy(C₁₋₃)alkoxy, benzyloxy (wherein the phenyl group is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂), C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, formyl, C₂₋₆ alkylcarbonyl, phenylcarbonyl (where the phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂), or R¹ and R² together are ═O, ═S, ═NR⁶⁰ or ═CR⁶¹R⁶², wherein R⁶⁰ is OH, C₁-C₆-alkoxy or C₁-C₆-alkylcarbonylamino, and R⁶¹ and R⁶² are independently H, C₁-C₆-alkyl, or C₁-C₆-haloalkyl; or R¹ and R⁹ together with the carbon atom they are attached form a three to six membered ring, that optionally may contain one or two not adjacent oxygen atoms; or R¹ and R² together form a three to six membered ring, that optionally may contain one or two non-adjacent oxygen atoms.

More preferably each R¹ and R² group is independently hydrogen, hydroxy, halogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkenyloxy, C₁₋₆ alkynyloxy, C₁₋₃ alkoxy(C₁₋₃)alkoxy or benzyloxy.

Most preferably each R¹ and R² group is independently hydrogen or methyl.

R⁹ is preferably hydrogen, C₁₋₆ alkyl, C₁₋₆ cyanoalkyl, C₁₋₆ haloalkyl, C₃₋₇ cycloalkyl(C₁₋₄alkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, aryl(C₁₋₆)alkyl (wherein the aryl group may be optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylthio, C₁₋₆ alkoxycarbonyl, C₁₋₆ alkylcarbonylamino, arylcarbonyl), C₂₋₆ alkylcarbonyl, phenylcarbonyl (where the phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino), C₁₋₆ alkoxycarbonyl, C(O)NR⁶³R⁶⁴ (where R⁶³ and R⁶⁴ are independently hydrogen, C₁₋₆ alkyl or C₁₋₆ haloalkyl or C₁₋₆ alkoxy(C₁₋₆)alkyl or R⁶³ and R⁶⁴ together with the N atom to which they are attached form a five, six or seven-membered ring containing an O or S atom), or R⁹ and R¹ together with the carbon atoms to which they are attached form a three to six membered ring.

More preferably R⁹ is independently hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₃₋₇ cycloalkyl(C₁₋₄)alkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, aryl(C₁₋₆)alkyl (wherein the aryl group may be optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy), C₂₋₆ alkylcarbonyl, phenylcarbonyl (where the phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl), C₁₋₆ alkoxycarbonyl, or R⁹ and R¹ together with the carbon atoms to which they are attached form a three to six membered ring.

Most preferably R₉ is independently hydrogen or methyl.

Preferably each R⁴ is independently halogen, cyano, C₁₋₈ alkyl, C₁₋₈ haloalkyl, cyano(C₁₋₆)alkyl, C₁₋₃ alkoxy(C₁₋₃)alkyl, C₂₋₆ alkynyl, C₃₋₆ cycloalkyl, C₁₋₃ alkyl (C₃₋₆) cycloalkyl, phenyl (optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino), heterocyclyl (optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆ haloalkoxy), formyl, C₁₋₆ alkylcarbonyl, C₁₋₆ alkoxycarbonyl, C₁₋₆ alkylthiocarbonyl, C₁₋₆ alkoxythiocarbonyl, carbamoyl, C₁₋₆ alkylaminocarbonyl, di-C₁₋₆ alkylaminocarbonyl, thiocarbamoyl, C₁₋₆ alkylaminothiocarbonyl, di-C₁₋₆ alkylaminothiocarbonyl, C₁₋₈ alkoxy, C₁₋₆ haloalkoxy, phenoxy (optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, phenyl), heteroaryloxy (optionally substituted by halo, nitro, cyano, C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy or C₁₋₃ haloalkoxy), C₁₋₆ alkylcarbonyloxy, C₁₋₆ alkoxycarbonyloxy, C₁₋₆ alkylaminocarbonyloxy, di-C₁₋₆ alkylaminocarbonyloxy, C₁₋₆ alkylaminothiocarbonyloxy, di-C₁₋₆ alkylaminothiocarbonyloxy, C₁₋₈ alkylthio, C₁₋₆ haloalkylthio, arylthio or heteroarylthio (where the aryl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂ or phenyl), C₁₋₆ alkylcarbonylthio, C₁₋₆ alkylaminocarbonylthio, di-C₁₋₆ alkylaminocarbonylthio, di(C₁₋₈)alkylamino, C₁₋₆ alkylcarbonylamino, C₁₋₆ alkoxycarbonylamino, C₁₋₆ alkylaminocarbonylamino, di-C₁₋₆ alkylaminocarbonylamino, aminothiocarbonylamino, C₁₋₆ alkylaminothiocarbonylamino, di-C₁₋₆ alkylaminothiocarbonylamino, or 2 adjacent groups R⁴ together with the carbon atoms to which they are attached form a 4, 5, 6 or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2 or 3.

More preferably each R⁴ is independently halogen, cyano, C₁₋₈ alkyl, C₁₋₈ haloalkyl, cyano(C₁₋₆)alkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₂₋₆ alkynyl, heterocyclyl (optionally substituted by C₁₋₆ alkyl), C₁₋₈ alkoxy, C₁₋₆ haloalkoxy, phenoxy (optionally substituted by halo, cyano, C₁₋₃ alkyl or C₁₋₃ haloalkyl), heteroaryloxy (optionally substituted by halo, cyano, C₁₋₃ alkyl or C₁₋₃ haloalkyl), C₁₋₃ alkoxy, C₁₋₃ haloalkoxy, C₁₋₃ alkylthio, C₁₋₃ haloalkylthio, C₁₋₃ alksulfonyl, di(C₁₋₈)alkylamino, or 2 adjacent groups R⁴ together with the carbon atoms to which they are attached form a 4, 5, 6 or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2 or 3.

Most preferably each R⁴ is independently fluoro, chloro, bromo, C₁₋₄ alkyl or C₁₋₄ haloalkyl; n is 1, 2 or 3, preferably 1 or 2.

Preferably at least one group R⁴ is positioned adjacent to the group Y.

R¹⁰ is preferably hydrogen, hydroxy, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, phenyl(C₁₋₃)alkyl (wherein the phenyl group may be optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino, dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl), C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₂₋₆ alkenyloxy, C₂₋₆ alkinyloxy, C₁₋₃ alkoxy(C₁₋₃)alkoxy, benzyloxy (wherein the phenyl group is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂), C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, phenylthio (where the phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂), C₁₋₆ alkyldithio, C₁₋₆ haloalkyldithio, formyl, C₂₋₆ alkylcarbonyl, C₂₋₆ haloalkylcarbonyl, C₁₋₆ alkoxycarbonyl, arylcarbonyl (where the aryl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂), NR⁶⁵R⁶⁶ (where R⁶⁵ and R⁶⁶ are independently hydrogen, C₁₋₆ alkyl or C₁₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆ alkylcarbonyl or R⁶⁵ and R⁶⁶ together with the N atom to which they are attached form a five, six or seven-membered ring containing an O or S atom), R⁶⁵R⁶⁶NS, R⁶⁵R⁶⁶NC(O), R⁶⁵R⁶⁶NC(S), R⁶⁷N═C(R⁶⁸)—, where R⁶⁷ is C₁₋₆ alkyl or phenyl (optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂), and R⁶⁸ is H, C₁₋₆ alkyl or C₁₋₆ alkylthio.

More preferably R¹⁰ is hydrogen, hydroxy, cyano, C₁₋₆ alkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆ alkoxy, C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, formyl, C₂₋₆ alkylcarbonyl, C₁₋₆ alkoxycarbonyl, NR⁶⁵R⁶⁶ (where R⁶⁵ and R⁶⁶ are independently hydrogen, C₁₋₆ alkyl or C₁₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆ alkylcarbonyl or R⁶⁵ and R⁶⁶ together with the N atom to which they are attached form a five, six or seven-membered ring containing an O or S atom).

Most preferably R¹⁰ is hydrogen, cyano, or formyl, especially hydrogen.

It is preferred that the ring

is a 6-membered aromatic ring or is 5 or 6 membered heteroaromatic ring wherein the ring members are each independently CH, S, N, NR⁴, O, or CR⁴ provided that there are no more than one O or S atoms present in the ring.

More preferably the ring

is a benzene, thiophene, furan, pyridine, pyrimidine, pyrazine, pyridazine, triazine, pyrrole, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, [1,2,3]triazole, [1,2,3]oxadiazole or [1,2,3]thiadiazole

Most preferably the ring

is a benzene, pyridine or thiophene ring, especially a benzene ring.

Another especially preferred group of compounds are those compounds of formula (IB)

where the chirality on the R⁹ bearing carbon atom is that shown in the above structure and R¹, R², R⁴, R⁹, R¹⁰, Y and n are as defined above in relation to formula (I).

Certain compounds of formula (I) are novel and as such form a further aspect of the invention. One group of novel compounds are compounds of formula IC

wherein R¹, R², R⁴, R⁹, T, X, Y and n are as defined in in claim 1 or salts or N-oxides thereof, with the proviso that the following compounds (IC1) to (IC3) are excluded:

wherein R¹⁰⁰ is hydrogen or acetyl, and

wherein R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ are hydrogen, R²⁰⁰ and R³⁰⁰ are independently of each other halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ alkylthio, trifluoromethyl or trifluoromethoxy, where s and t are independently of each other 0, 1, 2 or 3, and the total of s+t is not greater than 3.

A preferred group of new compounds of the formula IC are those of the formula ID

or salts or N-oxides thereof, wherein Y is CR⁵R⁶ or CR⁵R⁶CR⁷R⁸, and R¹, R², R⁴, R⁹, X and n are as defined above, where at least one of R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸ or R⁹ is fluorine, and those of formula IE

or salts or N-oxides thereof, wherein Y is CR⁵R⁶, and R¹, R², R⁴, R⁹, X are as defined above and n is 0, 1, 2 or 3.

The compounds in Tables I to LXIII below illustrate the compounds of the invention.

Table I provides 612 compounds of formula Ia

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

TABLE 1 Compound No R9 R1 R2 R7 R8 R4a R4b R4c R4d I-1 Me H H H H H H H H I-2 Et H H H H H H H H I-3 Vinyl H H H H H H H H I-4 Allyl H H H H H H H H I-5 cyclopropyl H H H H H H H H I-6 CN H H H H H H H H I-7 CONH₂ H H H H H H H H I-8 CONHMe H H H H H H H H I-9 CONMe₂ H H H H H H H H I-10 COMe H H H H H H H H I-11 COOH H H H H H H H H I-12 COOMe H H H H H H H H I-13 CSNHMe H H H H H H H H I-14 H Me H H H H H H H I-15 H Et H H H H H H H I-16 H vinyl H H H H H H H I-17 H allyl H H H H H H H I-18 H cyclopropyl H H H H H H H I-19 H F H H H H H H H I-20 H Cl H H H H H H H I-21 H NO₂ H H H H H H H I-22 H CN H H H H H H H I-23 H CONH₂ H H H H H H H I-24 H CONHMe H H H H H H H I-25 H CONMe₂ H H H H H H H I-26 H COMe H H H H H H H I-27 H COOH H H H H H H H I-28 H COOMe H H H H H H H I-29 H CSOMe H H H H H H H I-30 H CSNH₂ H H H H H H H I-31 H CSNMe₂ H H H H H H H I-32 H CSNHMe H H H H H H H I-33 H OMe H H H H H H H I-34 H OEt H H H H H H H I-35 H OCOMe H H H H H H H I-36 H OCOOMe H H H H H H H I-37 H OCONHMe H H H H H H H I-38 H OCONMe₂ H H H H H H H I-39 H OCSMe H H H H H H H I-40 H OCSNMe₂ H H H H H H H I-41 H SMe H H H H H H H I-42 H SEt H H H H H H H I-43 H SCOMe H H H H H H H I-44 H SCSNMe₂ H H H H H H H I-45 H SCSNHMe H H H H H H H I-46 H NHMe H H H H H H H I-47 H NH₂ H H H H H H H I-48 H NMe₂ H H H H H H H I-49 H NHCOMe H H H H H H H I-50 H NHCONH₂ H H H H H H H I-51 H NHCONHMe H H H H H H H I-52 H NHCONMe₂ H H H H H H H I-53 H phenyl H H H H H H H I-54 H 2-chloro- H H H H H H H phenyl I-55 H 4-nitrophenyl H H H H H H H I-56 H 2-pyridyl H H H H H H H I-57 H 3-pyridyl H H H H H H H I-58 H 4-pyridyl H H H H H H H I-59 H 2-furyl H H H H H H H I-60 H PhO H H H H H H H I-61 CH₂ H H H H H H H I-62 H ═O H H H H H H I-63 H ═NOH H H H H H H I-64 H ═NOMe H H H H H H I-65 H ═CH₂ H H H H H H I-66 H ═CHMe H H H H H H I-67 H H H H H H H H H I-68 H H H Me H H H H H I-69 H H H Et H H H H H I-70 H H H Vinyl H H H H H I-71 H H H Allyl H H H H H I-72 H H H cyclopropyl H H H H H I-73 H H H F H H H H H I-74 H H H Cl H H H H H I-75 H H H NO₂ H H H H H I-76 H H H CN H H H H H I-77 H H H CONH₂ H H H H H I-78 H H H CONHMe H H H H H I-79 H H H CONMe₂ H H H H H I-80 H H H COMe H H H H H I-81 H H H COOH H H H H H I-82 H H H COOMe H H H H H I-83 H H H CSOMe H H H H H I-84 H H H CSNH₂ H H H H H I-85 H H H CSNMe₂ H H H H H I-86 H H H CSNHMe H H H H H I-87 H H H OMe H H H H H I-88 H H H OEt H H H H H I-89 H H H OCOMe H H H H H I-90 H H H OCOOMe H H H H H I-91 H H H OCONHMe H H H H H I-92 H H H OCONMe₂ H H H H H I-93 H H H OCSMe H H H H H I-94 H H H OCSNMe₂ H H H H H I-95 H H H SMe H H H H H I-96 H H H SEt H H H H H I-97 H H H SCOMe H H H H H I-98 H H H SCSNMe₂ H H H H H I-99 H H H SCSNHMe H H H H H I-100 H H H NHMe H H H H H I-101 H H H NH₂ H H H H H I-102 H H H NMe₂ H H H H H I-103 H H H NHCOMe H H H H H I-104 H H H NHCONH₂ H H H H H I-105 H H H NHCONHMe H H H H H I-106 H H H NHCONMe₂ H H H H H I-107 H H H Phenyl H H H H H I-108 H H H 2-chloro- H H H H H phenyl I-109 H H H 4- H H H H H nitrophenyl I-110 H H H 2-pyridyl H H H H H I-111 H H H 3-pyridyl H H H H H I-112 H H H 4-pyridyl H H H H H I-113 H H H 2-furyl H H H H H I-114 H H H PhO H H H H H I-115 H H H ═O H H H H I-116 H H H ═NOH H H H H I-117 H H H ═NOMe H H H H I-118 H H H ═CH₂ H H H H I-119 H H H ═CHMe H H H H I-120 H Me H Me H H H H H I-121 H Me F Me H H H H H I-122 H Me H F H H H H H I-123 H Me F H H H H H H I-124 H Me Me H H H H H H I-125 H F H Me H H H H H I-126 H F H F H H H H H I-127 Me H H H H F H H H I-128 Et H H H H F H H H I-129 vinyl H H H H F H H H I-130 allyl H H H H F H H H I-131 cyclopropyl H H H H F H H H I-132 CN H H H H F H H H I-133 CONH₂ H H H H F H H H I-134 CONHMe H H H H F H H H I-135 CONMe₂ H H H H F H H H I-136 COMe H H H H F H H H I-137 COOH H H H H F H H H I-138 COOMe H H H H F H H H I-139 CSNHMe H H H H F H H H I-140 H Me H H H F H H H I-141 H Et H H H F H H H I-142 H vinyl H H H F H H H I-143 H allyl H H H F H H H I-144 H cyclopropyl H H H F H H H I-145 H F H H H F H H H I-146 H Cl H H H F H H H I-147 H NO₂ H H H F H H H I-148 H CN H H H F H H H I-149 H CONH₂ H H H F H H H I-150 H CONHMe H H H F H H H I-151 H CONMe₂ H H H F H H H I-152 H COMe H H H F H H H I-153 H COOH H H H F H H H I-154 H COOMe H H H F H H H I-155 H CSOMe H H H F H H H I-156 H CSNH₂ H H H F H H H I-157 H CSNMe₂ H H H F H H H I-158 H CSNHMe H H H F H H H I-159 H OMe H H H F H H H I-160 H OEt H H H F H H H I-161 H OCOMe H H H F H H H I-162 H OCOOMe H H H F H H H I-163 H OCONHMe H H H F H H H I-164 H OCONMe₂ H H H F H H H I-165 H OCSMe H H H F H H H I-166 H OCSNMe₂ H H H F H H H I-167 H SMe H H H F H H H I-168 H SEt H H H F H H H I-169 H SCOMe H H H F H H H I-170 H SCSNMe₂ H H H F H H H I-171 H SCSNHMe H H H F H H H I-172 H NHMe H H H F H H H I-173 H NH₂ H H H F H H H I-174 H NMe₂ H H H F H H H I-175 H NHCOMe H H H F H H H I-176 H NHCONH₂ H H H F H H H I-177 H NHCONHMe H H H F H H H I-178 H NHCONMe₂ H H H F H H H I-179 H phenyl H H H F H H H I-180 H 2-chloro- H H H F H H H phenyl I-181 H 4-nitrophenyl H H H F H H H I-182 H 2-pyridyl H H H F H H H I-183 H 3-pyridyl H H H F H H H I-184 H 4-pyridyl H H H F H H H I-185 H 2-furyl H H H F H H H I-186 H PhO H H H F H H H I-187 CH₂ H H H F H H H I-188 H H H Me H F H H H I-190 H H H Vinyl H F H H H I-191 H H H Allyl H F H H H I-192 H H H Cyclopropyl H F H H H I-193 H H H F H F H H H I-194 H H H Cl H F H H H I-195 H H H NO₂ H F H H H I-196 H H H CN H F H H H I-197 H H H CONH₂ H F H H H I-198 H H H CONHMe H F H H H I-199 H H H CONMe₂ H F H H H I-200 H H H COMe H F H H H I-201 H H H COOH H F H H H I-202 H H H COOMe H F H H H I-203 H H H CSOMe H F H H H I-204 H H H CSNH₂ H F H H H I-205 H H H CSNMe₂ H F H H H I-206 H H H CSNHMe H F H H H I-207 H H H OMe H F H H H I-208 H H H OEt H F H H H I-209 H H H OCOMe H F H H H I-210 H H H OCOOMe H F H H H I-211 H H H OCONHMe H F H H H I-212 H H H OCONMe₂ H F H H H I-213 H H H OCSMe H F H H H I-214 H H H OCSNMe2 H F H H H I-215 H H H SMe H F H H H I-216 H H H SEt H F H H H I-217 H H H SCOMe H F H H H I-218 H H H SCSNMe₂ H F H H H I-219 H H H SCSNHMe H F H H H I-220 H H H NHMe H F H H H I-221 H H H NH₂ H F H H H I-222 H H H NMe₂ H F H H H I-223 H H H NHCOMe H F H H H I-224 H H H NHCONH₂ H F H H H I-225 H H H NHCONHMe H F H H H I-226 H H H NHCONMe₂ H F H H H I-227 H H H Phenyl H F H H H I-228 H H H 2-chloro- H F H H H phenyl I-229 H H H 4-nitrophenyl H F H H H I-230 H H H 2-pyridyl H F H H H I-231 H H H 3-pyridyl H F H H H I-232 H H H 4-pyridyl H F H H H I-233 H H H 2-furyl H F H H H I-234 H H H PhO H F H H H I-235 H Me H Me H F H H H I-236 H Me F Me H F H H H I-237 H Me H F H F H H H I-238 H Me F H H F H H H I-239 H Me Me H H F H H H I-240 H F H Me H F H H H I-241 H F H F H F H H H I-242 Me H H H H Me H H H I-243 Et H H H H Me H H H I-244 vinyl H H H H Me H H H I-245 allyl H H H H Me H H H I-246 cyclopropyl H H H H Me H H H I-247 CN H H H H Me H H H I-248 CONH₂ H H H H Me H H H I-249 CONHMe H H H H Me H H H I-250 CONMe₂ H H H H Me H H H I-251 COMe H H H H Me H H H I-252 COOH H H H H Me H H H I-253 COOMe H H H H Me H H H I-254 CSNHMe H H H H Me H H H I-255 H Me H H H Me H H H I-256 H Et H H H Me H H H I-257 H vinyl H H H Me H H H I-258 H allyl H H H Me H H H I-259 H cyclopropyl H H H Me H H H I-260 H F H H H Me H H H I-261 H Cl H H H Me H H H I-262 H NO₂ H H H Me H H H I-263 H CN H H H Me H H H I-264 H CONH₂ H H H Me H H H I-265 H CONHMe H H H Me H H H I-266 H CONMe₂ H H H Me H H H I-267 H COMe H H H Me H H H I-268 H COOH H H H Me H H H I-269 H COOMe H H H Me H H H I-270 H CSOMe H H H Me H H H I-271 H CSNH₂ H H H Me H H H I-272 H CSNMe₂ H H H Me H H H I-273 H CSNHMe H H H Me H H H I-274 H OMe H H H Me H H H I-275 H OEt H H H Me H H H I-276 H OCOMe H H H Me H H H I-277 H OCOOMe H H H Me H H H I-278 H OCONHMe H H H Me H H H I-279 H OCONMe₂ H H H Me H H H I-280 H OCSMe H H H Me H H H I-281 H OCSNMe₂ H H H Me H H H I-282 H SMe H H H Me H H H I-283 H SEt H H H Me H H H I-284 H SCOMe H H H Me H H H I-285 H SCSNMe₂ H H H Me H H H I-286 H SCSNHMe H H H Me H H H I-287 H NHMe H H H Me H H H I-288 H NH₂ H H H Me H H H I-289 H NMe₂ H H H Me H H H I-290 H NHCOMe H H H Me H H H I-291 H NHCONH₂ H H H Me H H H I-292 H NHCONHMe H H H Me H H H I-293 H NHCONMe₂ H H H Me H H H I-294 H phenyl H H H Me H H H I-295 H 2-chloro- H H H Me H H H phenyl I-296 H 4-nitrophenyl H H H Me H H H I-297 H 2-pyridyl H H H Me H H H I-298 H 3-pyridyl H H H Me H H H I-299 H 4-pyridyl H H H Me H H H I-300 H 2-furyl H H H Me H H H I-301 H PhO H H H Me H H H I-302 CH₂ H H H Me H H H I-303 H H H Me H Me H H H I-304 H H H Et H Me H H H I-305 H H H Vinyl H Me H H H I-306 H H H Allyl H Me H H H I-307 H H H Cyclopropyl H Me H H H I-308 H H H F H Me H H H I-309 H H H Cl H Me H H H I-310 H H H NO₂ H Me H H H I-311 H H H CN H Me H H H I-312 H H H CONH₂ H Me H H H I-313 H H H CONHMe H Me H H H I-314 H H H CONMe₂ H Me H H H I-315 H H H COMe H Me H H H I-316 H H H COOH H Me H H H I-317 H H H COOMe H Me H H H I-318 H H H CSOMe H Me H H H I-319 H H H CSNH₂ H Me H H H I-320 H H H CSNMe₂ H Me H H H I-321 H H H CSNHMe H Me H H H I-322 H H H OMe H Me H H H I-323 H H H OEt H Me H H H I-324 H H H OCOMe H Me H H H I-325 H H H OCOOMe H Me H H H I-326 H H H OCONHMe H Me H H H I-327 H H H OCONMe₂ H Me H H H I-328 H H H OCSMe H Me H H H I-329 H H H OCSNMe2 H Me H H H I-330 H H H SMe H Me H H H I-331 H H H SEt H Me H H H I-332 H H H SCOMe H Me H H H I-333 H H H SCSNMe₂ H Me H H H I-334 H H H SCSNHMe H Me H H H I-335 H H H NHMe H Me H H H I-336 H H H NH₂ H Me H H H I-337 H H H NMe₂ H Me H H H I-338 H H H NHCOMe H Me H H H I-339 H H H NHCONH₂ H Me H H H I-340 H H H NHCONHMe H Me H H H I-341 H H H NHCONMe₂ H Me H H H I-342 H H H Phenyl H Me H H H I-343 H H H 2-chloro- H Me H H H phenyl I-344 H H H 4-nitrophenyl H Me H H H I-345 H H H 2-pyridyl H Me H H H I-346 H H H 3-pyridyl H Me H H H I-347 H H H 4-pyridyl H Me H H H I-348 H H H 2-furyl H Me H H H I-349 H H H PhO H Me H H H I-350 H Me H Me H Me H H H I-351 H Me F Me H Me H H H I-352 H Me H F H Me H H H I-353 H Me F H H Me H H H I-354 H Me Me H H Me H H H I-355 H F H Me H Me H H H I-356 H F H F H Me H H H I-357 Me H H H H F H F H I-358 Et H H H H F H F H I-359 vinyl H H H H F H F H I-360 allyl H H H H F H F H I-361 cyclopropyl H H H H F H F H I-362 CN H H H H F H F H I-363 CONH₂ H H H H F H F H I-364 CONHMe H H H H F H F H I-365 CONMe₂ H H H H F H F H I-366 COMe H H H H F H F H I-367 COOH H H H H F H F H I-368 COOMe H H H H F H F H I-369 CSNHMe H H H H F H F H I-370 H Me H H H F H F H I-371 H Et H H H F H F H I-372 H vinyl H H H F H F H I-373 H allyl H H H F H F H I-374 H cyclopropyl H H H F H F H I-375 H F H H H F H F H I-376 H Cl H H H F H F H I-377 H NO₂ H H H F H F H I-378 H CN H H H F H F H I-379 H CONH₂ H H H F H F H I-380 H CONHMe H H H F H F H I-381 H CONMe₂ H H H F H F H I-382 H COMe H H H F H F H I-383 H COOH H H H F H F H I-384 H COOMe H H H F H F H I-385 H CSOMe H H H F H F H I-386 H CSNH₂ H H H F H F H I-387 H CSNMe₂ H H H F H F H I-388 H CSNHMe H H H F H F H I-389 H OMe H H H F H F H I-390 H OEt H H H F H F H I-391 H OCOMe H H H F H F H I-392 H OCOOMe H H H F H F H I-393 H OCONHMe H H H F H F H I-394 H OCONMe₂ H H H F H F H I-395 H OCSMe H H H F H F H I-396 H OCSNMe₂ H H H F H F H I-397 H SMe H H H F H F H I-398 H SEt H H H F H F H I-399 H SCOMe H H H F H F H I-400 H SCSNMe₂ H H H F H F H I-401 H SCSNHMe H H H F H F H I-402 H NHMe H H H F H F H I-403 H NH₂ H H H F H F H I-404 H NMe₂ H H H F H F H I-405 H NHCOMe H H H F H F H I-406 H NHCONH₂ H H H F H F H I-407 H NHCONHMe H H H F H F H I-408 H NHCONMe₂ H H H F H F H I-409 H phenyl H H H F H F H I-410 H 2-chloro- H H H F H F H phenyl I-411 H 4- H H H F H F H nitrophenyl I-412 H 2-pyridyl H H H F H F H I-413 H 3-pyridyl H H H F H F H I-414 H 4-pyridyl H H H F H F H I-415 H 2-furyl H H H F H F H I-416 H PhO H H H F H F H I-417 CH₂ H H H F H F H I-418 H H H Me H F H F H I-419 H H H Et H F H F H I-420 H H H Vinyl H F H F H I-421 H H H Allyl H F H F H I-422 H H H Cyclopropyl H F H F H I-423 H H H F H F H F H I-424 H H H Cl H F H F H I-425 H H H NO₂ H F H F H I-426 H H H CN H F H F H I-427 H H H CONH₂ H F H F H I-428 H H H CONHMe H F H F H I-429 H H H CONMe₂ H F H F H I-430 H H H COMe H F H F H I-431 H H H COOH H F H F H I-432 H H H COOMe H F H F H I-433 H H H CSOMe H F H F H I-434 H H H CSNH₂ H F H F H I-435 H H H CSNMe₂ H F H F H I-436 H H H CSNHMe H F H F H I-437 H H H OMe H F H F H I-438 H H H OEt H F H F H I-439 H H H OCOMe H F H F H I-440 H H H OCOOMe H F H F H I-441 H H H OCONHMe H F H F H I-442 H H H OCONMe₂ H F H F H I-443 H H H OCSMe H F H F H I-444 H H H OCSNMe₂ H F H F H I-445 H H H SMe H F H F H I-446 H H H SEt H F H F H I-447 H H H SCOMe H F H F H I-448 H H H SCSNMe₂ H F H F H I-449 H H H SCSNHMe H F H F H I-450 H H H NHMe H F H F H I-451 H H H NH₂ H F H F H I-452 H H H NMe₂ H F H F H I-453 H H H NHCOMe H F H F H I-454 H H H NHCONH₂ H F H F H I-455 H H H NHCONHMe H F H F H I-456 H H H NHCONMe₂ H F H F H I-457 H H H Phenyl H F H F H I-458 H H H 2-chloro- H F H F H phenyl I-459 H H H 4-nitrophenyl H F H F H I-460 H H H 2-pyridyl H F H F H I-461 H H H 3-pyridyl H F H F H I-462 H H H 4-pyridyl H F H F H I-463 H H H 2-furyl H F H F H I-464 H H H PhO H F H F H I-465 H Me H Me H F H F H I-466 H Me F Me H F H F H I-467 H Me H F H F H F H I-468 H Me F H H F H F H I-469 H Me Me H H F H F H I-470 H F H Me H F H F H I-471 H F H F H F H F H I-472 H H H H H Me H H H I-473 H H H H H Et H H H I-474 H H H H H vinyl H H H I-475 H H H H H allyl H H H I-476 H H H H H cyclopropyl H H H I-477 H H H H H F H H H I-478 H H H H H Cl H H H I-479 H H H H H NO₂ H H H I-480 H H H H H CN H H H I-481 H H H H H CONH₂ H H H I-482 H H H H H CONHMe H H H I-483 H H H H H CONMe₂ H H H I-484 H H H H H COMe H H H I-485 H H H H H COOH H H H I-486 H H H H H COOMe H H H I-487 H H H H H CSOMe H H H I-488 H H H H H CSNH₂ H H H I-489 H H H H H CSNMe₂ H H H I-490 H H H H H CSNHMe H H H I-491 H H H H H OMe H H H I-492 H H H H H OEt H H H I-493 H H H H H OCOMe H H H I-494 H H H H H OCOOMe H H H I-495 H H H H H OCONHMe H H H I-496 H H H H H OCONMe₂ H H H I-497 H H H H H OCSMe H H H I-498 H H H H H OCSNMe₂ H H H I-499 H H H H H SMe H H H I-500 H H H H H SEt H H H I-501 H H H H H SCOMe H H H I-502 H H H H H SCSNMe₂ H H H I-503 H H H H H SCSNHMe H H H I-504 H H H H H NHMe H H H I-505 H H H H H NH₂ H H H I-506 H H H H H NMe₂ H H H I-507 H H H H H NHCOMe H H H I-508 H H H H H NHCONH₂ H H H I-509 H H H H H NHCONHMe H H H I-510 H H H H H NHCONMe₂ H H H I-511 H H H H H phenyl H H H I-512 H H H H H 2-chloro- H H H phenyl I-513 H H H H H 4- H H H nitrophenyl I-514 H H H H H 2-pyridyl H H H I-515 H H H H H 3-pyridyl H H H I-516 H H H H H 4-pyridyl H H H I-517 H H H H H 2-furyl H H H I-518 H H H H H PhO H H H I-519 H H H H H H H Me H I-520 H H H H H H H Et H I-521 H H H H H H H vinyl H I-522 H H H H H H H allyl H I-523 H H H H H H H cyclopropyl H I-524 H H H H H H H F H I-525 H H H H H H H Cl H I-526 H H H H H H H NO₂ H I-527 H H H H H H H CN H I-528 H H H H H H H CONH₂ H I-529 H H H H H H H CONHMe H I-530 H H H H H H H CONMe₂ H I-531 H H H H H H H COMe H I-532 H H H H H H H COOH H I-533 H H H H H H H COOMe H I-534 H H H H H H H CSOMe H I-535 H H H H H H H CSNH₂ H I-536 H H H H H H H CSNMe₂ H I-537 H H H H H H H CSNHMe H I-538 H H H H H H H OMe H I-539 H H H H H H H OEt H I-540 H H H H H H H OCOMe H I-541 H H H H H H H OCOOMe H I-542 H H H H H H H OCONHMe H I-543 H H H H H H H OCONMe₂ H I-544 H H H H H H H OCSMe H I-545 H H H H H H H OCSNMe₂ H I-546 H H H H H H H SMe H I-547 H H H H H H H SEt H I-548 H H H H H H H SCOMe H I-549 H H H H H H H SCSNMe₂ H I-550 H H H H H H H SCSNHMe H I-551 H H H H H H H NHMe H I-552 H H H H H H H NH₂ H I-553 H H H H H H H NMe₂ H I-554 H H H H H H H NHCOMe H I-555 H H H H H H H NHCONH₂ H I-556 H H H H H H H NHCONHMe H I-557 H H H H H H H NHCONMe₂ H I-558 H H H H H H H phenyl H I-559 H H H H H H H 2- H chloro- phenyl I-560 H H H H H H H 4- H nitrophenyl I-561 H H H H H H H 2- H pyridyl I-562 H H H H H H H 3- H pyridyl I-563 H H H H H H H 4- H pyridyl I-564 H H H H H H H 2-furyl H I-565 H H H H H H H PhO H I-566 H H H H H H H H Me I-567 H H H H H H H H Et I-568 H H H H H H H H vinyl I-569 H H H H H H H H allyl I-570 H H H H H H H H cyclopropyl I-571 H H H H H H H H F I-572 H H H H H H H H Cl I-573 H H H H H H H H NO₂ I-574 H H H H H H H H CN I-575 H H H H H H H H CONH₂ I-576 H H H H H H H H CONHMe I-577 H H H H H H H H CONMe₂ I-578 H H H H H H H H COMe I-579 H H H H H H H H COOH I-580 H H H H H H H H COOMe I-581 H H H H H H H H CSOMe I-582 H H H H H H H H CSNH₂ I-583 H H H H H H H H CSNMe₂ I-584 H H H H H H H H CSNHMe I-585 H H H H H H H H OMe I-586 H H H H H H H H OEt I-587 H H H H H H H H OCOMe I-588 H H H H H H H H OCOOMe I-589 H H H H H H H H OCONHMe I-590 H H H H H H H H OCONMe₂ I-591 H H H H H H H H OCSMe I-592 H H H H H H H H OCSNMe₂ I-593 H H H H H H H H SMe I-594 H H H H H H H H SEt I-595 H H H H H H H H SCOMe I-596 H H H H H H H H SCSNMe₂ I-597 H H H H H H H H SCSNHMe I-598 H H H H H H H H NHMe I-599 H H H H H H H H NH₂ I-600 H H H H H H H H NMe₂ I-601 H H H H H H H H NHCOMe I-602 H H H H H H H H NHCONH₂ I-603 H H H H H H H H NHCONHMe I-604 H H H H H H H H NHCONMe₂ I-605 H H H H H H H H phenyl I-606 H H H H H H H H 2-chloro- phenyl I-607 H H H H H H H H 4- nitrophenyl I-608 H H H H H H H H 2-pyridyl I-609 H H H H H H H H 3-pyridyl I-610 H H H H H H H H 4-pyridyl I-611 H H H H H H H H 2-furyl I-612 H H H H H H H H PhO

Table II provides 612 compounds of formula Ib

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table III provides 612 compounds of formula Ic

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table IV provides 612 compounds of formula Id

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table V provides 612 compounds of formula Ie

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table VI provides 612 compounds of formula If

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table VII provides 612 compounds of formula Ig

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table VIII provides 612 compounds of formula Ih

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table IX provides 612 compounds of formula II

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table X provides 612 compounds of formula Ij

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table XI provides 612 compounds of formula Ik

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table XII provides 612 compounds of formula Il

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table XIII provides 612 compounds of formula Im

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table XIV provides 612 compounds of formula In

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table XV provides 612 compounds of formula Io

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table XVI provides 612 compounds of formula Ip

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁷, R⁸ and R⁹ are given in Table 1.

Table XVII provides 612 compounds of formula Iq

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

TABLE 2 Compound No R9 R1 R2 R5 R6 R4a R4b R4c R4d XVII-1 Me H H H H H H H H XVII-2 Et H H H H H H H H XVII-3 vinyl H H H H H H H H XVII-4 allyl H H H H H H H H XVII-5 cyclopropyl H H H H H H H H XVII-6 CN H H H H H H H H XVII-7 CONH₂ H H H H H H H H XVII-8 CONHMe H H H H H H H H XVII-9 CONMe₂ H H H H H H H H XVII-10 COMe H H H H H H H H XVII-11 COOH H H H H H H H H XVII-12 COOMe H H H H H H H H XVII-13 CSNHMe H H H H H H H H XVII-14 H Me H H H H H H H XVII-15 H Et H H H H H H H XVII-16 H vinyl H H H H H H H XVII-17 H allyl H H H H H H H XVII-18 H cyclopropyl H H H H H H H XVII-19 H F H H H H H H H XVII-20 H Cl H H H H H H H XVII-21 H NO₂ H H H H H H H XVII-22 H CN H H H H H H H XVII-23 H CONH₂ H H H H H H H XVII-24 H CONHMe H H H H H H H XVII-25 H CONMe₂ H H H H H H H XVII-26 H COMe H H H H H H H XVII-27 H COOH H H H H H H H XVII-28 H COOMe H H H H H H H XVII-29 H CSOMe H H H H H H H XVII-30 H CSNH₂ H H H H H H H XVII-31 H CSNMe₂ H H H H H H H XVII-32 H CSNHMe H H H H H H H XVII-33 H OMe H H H H H H H XVII-34 H OEt H H H H H H H XVII-35 H OCOMe H H H H H H H XVII-36 H OCOOMe H H H H H H H XVII-37 H OCONHMe H H H H H H H XVII-38 H OCONMe₂ H H H H H H H XVII-39 H OCSMe H H H H H H H XVII-40 H OCSNMe₂ H H H H H H H XVII-41 H SMe H H H H H H H XVII-42 H SEt H H H H H H H XVII-43 H SCOMe H H H H H H H XVII-44 H SCSNMe₂ H H H H H H H XVII-45 H SCSNHMe H H H H H H H XVII-46 H NHMe H H H H H H H XVII-47 H NH₂ H H H H H H H XVII-48 H NMe₂ H H H H H H H XVII-49 H NHCOMe H H H H H H H XVII-50 H NHCONH₂ H H H H H H H XVII-51 H NHCONHMe H H H H H H H XVII-52 H NHCONMe₂ H H H H H H H XVII-53 H phenyl H H H H H H H XVII-54 H 2-chloro- H H H H H H H phenyl XVII-55 H 4-nitrophenyl H H H H H H H XVII-56 H 2-pyridyl H H H H H H H XVII-57 H 3-pyridyl H H H H H H H XVII-58 H 4-pyridyl H H H H H H H XVII-59 H 2-furyl H H H H H H H XVII-60 H PhO H H H H H H H XVII-61 CH₂ H H H H H H H XVII-62 H ═O H H H H H H XVII-63 H ═NOH H H H H H H XVII-64 H ═NOMe H H H H H H XVII-65 H ═CH₂ H H H H H H XVII-66 H ═CHMe H H H H H H XVII-67 H H H H H H H H H XVII-68 H H H Me H H H H H XVII-69 H H H Et H H H H H XVII-70 H H H vinyl H H H H H XVII-71 H H H allyl H H H H H XVII-72 H H H cyclopropyl H H H H H XVII-73 H H H F H H H H H XVII-74 H H H Cl H H H H H XVII-75 H H H NO₂ H H H H H XVII-76 H H H CN H H H H H XVII-77 H H H CONH₂ H H H H H XVII-78 H H H CONHMe H H H H H XVII-79 H H H CONMe₂ H H H H H XVII-80 H H H COMe H H H H H XVII-81 H H H COOH H H H H H XVII-82 H H H COOMe H H H H H XVII-83 H H H CSOMe H H H H H XVII-84 H H H CSNH₂ H H H H H XVII-85 H H H CSNMe₂ H H H H H XVII-86 H H H CSNHMe H H H H H XVII-87 H H H OMe H H H H H XVII-88 H H H OEt H H H H H XVII-89 H H H OCOMe H H H H H XVII-90 H H H OCOOMe H H H H H XVII-91 H H H OCONHMe H H H H H XVII-92 H H H OCONMe₂ H H H H H XVII-93 H H H OCSMe H H H H H XVII-94 H H H OCSNMe₂ H H H H H XVII-95 H H H SMe H H H H H XVII-96 H H H SEt H H H H H XVII-97 H H H SCOMe H H H H H XVII-98 H H H SCSNMe₂ H H H H H XVII-99 H H H SCSNHMe H H H H H XVII-100 H H H NHMe H H H H H XVII-101 H H H NH₂ H H H H H XVII-102 H H H NMe₂ H H H H H XVII-103 H H H NHCOMe H H H H H XVII-104 H H H NHCONH₂ H H H H H XVII-105 H H H NHCONHMe H H H H H XVII-106 H H H NHCONMe₂ H H H H H XVII-107 H H H phenyl H H H H H XVII-108 H H H 2-chloro- H H H H H phenyl XVII-109 H H H 4- H H H H H nitrophenyl XVII-110 H H H 2-pyridyl H H H H H XVII-111 H H H 3-pyridyl H H H H H XVII-112 H H H 4-pyridyl H H H H H XVII-113 H H H 2-furyl H H H H H XVII-114 H H H PhO H H H H H XVII-115 H H H ═O H H H H XVII-116 H H H ═NOH H H H H XVII-117 H H H ═NOMe H H H H XVII-118 H H H ═CH₂ H H H H XVII-119 H H H ═CHMe H H H H XVII-120 H Me H Me H H H H H XVII-121 H Me F Me H H H H H XVII-122 H Me H F H H H H H XVII-123 H Me F H H H H H H XVII-124 H Me Me H H H H H H XVII-125 H F H Me H H H H H XVII-126 H F H F H H H H H XVII-127 Me H H H H F H H H XVII-128 Et H H H H F H H H XVII-129 vinyl H H H H F H H H XVII-130 allyl H H H H F H H H XVII-131 cyclopropyl H H H H F H H H XVII-132 CN H H H H F H H H XVII-133 CONH₂ H H H H F H H H XVII-134 CONHMe H H H H F H H H XVII-135 CONMe₂ H H H H F H H H XVII-136 COMe H H H H F H H H XVII-137 COOH H H H H F H H H XVII-138 COOMe H H H H F H H H XVII-139 CSNHMe H H H H F H H H XVII-140 H Me H H H F H H H XVII-141 H Et H H H F H H H XVII-142 H vinyl H H H F H H H XVII-143 H allyl H H H F H H H XVII-144 H cyclopropyl H H H F H H H XVII-145 H F H H H F H H H XVII-146 H Cl H H H F H H H XVII-147 H NO₂ H H H F H H H XVII-148 H CN H H H F H H H XVII-149 H CONH₂ H H H F H H H XVII-150 H CONHMe H H H F H H H XVII-151 H CONMe₂ H H H F H H H XVII-152 H COMe H H H F H H H XVII-153 H COOH H H H F H H H XVII-154 H COOMe H H H F H H H XVII-155 H CSOMe H H H F H H H XVII-156 H CSNH₂ H H H F H H H XVII-157 H CSNMe₂ H H H F H H H XVII-158 H CSNHMe H H H F H H H XVII-159 H OMe H H H F H H H XVII-160 H OEt H H H F H H H XVII-161 H OCOMe H H H F H H H XVII-162 H OCOOMe H H H F H H H XVII-163 H OCONHMe H H H F H H H XVII-164 H OCONMe₂ H H H F H H H XVII-165 H OCSMe H H H F H H H XVII-166 H OCSNMe₂ H H H F H H H XVII-167 H SMe H H H F H H H XVII-168 H SEt H H H F H H H XVII-169 H SCOMe H H H F H H H XVII-170 H SCSNMe₂ H H H F H H H XVII-171 H SCSNHMe H H H F H H H XVII-172 H NHMe H H H F H H H XVII-173 H NH₂ H H H F H H H XVII-174 H NMe₂ H H H F H H H XVII-175 H NHCOMe H H H F H H H XVII-176 H NHCONH₂ H H H F H H H XVII-177 H NHCONHMe H H H F H H H XVII-178 H NHCONMe₂ H H H F H H H XVII-179 H phenyl H H H F H H H XVII-180 H 2-chloro- H H H F H H H phenyl XVII-181 H 4-nitrophenyl H H H F H H H XVII-182 H 2-pyridyl H H H F H H H XVII-183 H 3-pyridyl H H H F H H H XVII-184 H 4-pyridyl H H H F H H H XVII-185 H 2-furyl H H H F H H H XVII-186 H PhO H H H F H H H XVII-187 CH₂ H H H F H H H XVII-188 H H H Me H F H H H XVII-189 H H H Et H F H H H XVII-190 H H H vinyl H F H H H XVII-191 H H H allyl H F H H H XVII-192 H H H cyclopropyl H F H H H XVII-193 H H H F H F H H H XVII-194 H H H Cl H F H H H XVII-195 H H H NO₂ H F H H H XVII-196 H H H CN H F H H H XVII-197 H H H CONH₂ H F H H H XVII-198 H H H CONHMe H F H H H XVII-199 H H H CONMe₂ H F H H H XVII-200 H H H COMe H F H H H XVII-201 H H H COOH H F H H H XVII-202 H H H COOMe H F H H H XVII-203 H H H CSOMe H F H H H XVII-204 H H H CSNH₂ H F H H H XVII-205 H H H CSNMe₂ H F H H H XVII-206 H H H CSNHMe H F H H H XVII-207 H H H OMe H F H H H XVII-208 H H H OEt H F H H H XVII-209 H H H OCOMe H F H H H XVII-210 H H H OCOOMe H F H H H XVII-211 H H H OCONHMe H F H H H XVII-212 H H H OCONMe₂ H F H H H XVII-213 H H H OCSMe H F H H H XVII-214 H H H OCSNMe₂ H F H H H XVII-215 H H H SMe H F H H H XVII-216 H H H SEt H F H H H XVII-217 H H H SCOMe H F H H H XVII-218 H H H SCSNMe₂ H F H H H XVII-219 H H H SCSNHMe H F H H H XVII-220 H H H NHMe H F H H H XVII-221 H H H NH₂ H F H H H XVII-222 H H H NMe₂ H F H H H XVII-223 H H H NHCOMe H F H H H XVII-224 H H H NHCONH₂ H F H H H XVII-225 H H H NHCONHMe H F H H H XVII-226 H H H NHCONMe₂ H F H H H XVII-227 H H H phenyl H F H H H XVII-228 H H H 2-chloro- H F H H H phenyl XVII-229 H H H 4- H F H H H nitrophenyl XVII-230 H H H 2-pyridyl H F H H H XVII-231 H H H 3-pyridyl H F H H H XVII-232 H H H 4-pyridyl H F H H H XVII-233 H H H 2-furyl H F H H H XVII-234 H H H PhO H F H H H XVII-235 H Me H Me H F H H H XVII-236 H Me F Me H F H H H XVII-237 H Me H F H F H H H XVII-238 H Me F H H F H H H XVII-239 H Me Me H H F H H H XVII-240 H F H Me H F H H H XVII-241 H F H F H F H H H XVII-242 Me H H H H Me H H H XVII-243 Et H H H H Me H H H XVII-244 vinyl H H H H Me H H H XVII-245 allyl H H H H Me H H H XVII-246 cyclopropyl H H H H Me H H H XVII-247 CN H H H H Me H H H XVII-248 CONH₂ H H H H Me H H H XVII-249 CONHMe H H H H Me H H H XVII-250 CONMe₂ H H H H Me H H H XVII-251 COMe H H H H Me H H H XVII-252 COOH H H H H Me H H H XVII-253 COOMe H H H H Me H H H XVII-254 CSNHMe H H H H Me H H H XVII-255 H Me H H H Me H H H XVII-256 H Et H H H Me H H H XVII-257 H vinyl H H H Me H H H XVII-258 H allyl H H H Me H H H XVII-259 H cyclopropyl H H H Me H H H XVII-260 H F H H H Me H H H XVII-261 H Cl H H H Me H H H XVII-262 H NO₂ H H H Me H H H XVII-263 H CN H H H Me H H H XVII-264 H CONH₂ H H H Me H H H XVII-265 H CONHMe H H H Me H H H XVII-266 H CONMe₂ H H H Me H H H XVII-267 H COMe H H H Me H H H XVII-268 H COOH H H H Me H H H XVII-269 H COOMe H H H Me H H H XVII-270 H CSOMe H H H Me H H H XVII-271 H CSNH₂ H H H Me H H H XVII-272 H CSNMe₂ H H H Me H H H XVII-273 H CSNHMe H H H Me H H H XVII-274 H OMe H H H Me H H H XVII-275 H OEt H H H Me H H H XVII-276 H OCOMe H H H Me H H H XVII-277 H OCOOMe H H H Me H H H XVII-278 H OCONHMe H H H Me H H H XVII-279 H OCONMe₂ H H H Me H H H XVII-280 H OCSMe H H H Me H H H XVII-281 H OCSNMe2 H H H Me H H H XVII-282 H SMe H H H Me H H H XVII-283 H SEt H H H Me H H H XVII-284 H SCOMe H H H Me H H H XVII-285 H SCSNMe₂ H H H Me H H H XVII-286 H SCSNHMe H H H Me H H H XVII-287 H NHMe H H H Me H H H XVII-288 H NH₂ H H H Me H H H XVII-289 H NMe₂ H H H Me H H H XVII-290 H NHCOMe H H H Me H H H XVII-291 H NHCONH₂ H H H Me H H H XVII-292 H NHCONHMe H H H Me H H H XVII-293 H NHCONMe₂ H H H Me H H H XVII-294 H phenyl H H H Me H H H XVII-295 H 2-chloro- H H H Me H H H phenyl XVII-296 H 4-nitrophenyl H H H Me H H H XVII-297 H 2-pyridyl H H H Me H H H XVII-298 H 3-pyridyl H H H Me H H H XVII-299 H 4-pyridyl H H H Me H H H XVII-300 H 2-furyl H H H Me H H H XVII-301 H PhO H H H Me H H H XVII-302 CH₂ H H H Me H H H XVII-303 H H H Me H Me H H H XVII-304 H H H Et H Me H H H XVII-305 H H H vinyl H Me H H H XVII-306 H H H allyl H Me H H H XVII-307 H H H cyclopropyl H Me H H H XVII-308 H H H F H Me H H H XVII-309 H H H Cl H Me H H H XVII-310 H H H NO₂ H Me H H H XVII-311 H H H CN H Me H H H XVII-312 H H H CONH₂ H Me H H H XVII-313 H H H CONHMe H Me H H H XVII-314 H H H CONMe₂ H Me H H H XVII-315 H H H COMe H Me H H H XVII-316 H H H COOH H Me H H H XVII-317 H H H COOMe H Me H H H XVII-318 H H H CSOMe H Me H H H XVII-319 H H H CSNH₂ H Me H H H XVII-320 H H H CSNMe₂ H Me H H H XVII-321 H H H CSNHMe H Me H H H XVII-322 H H H OMe H Me H H H XVII-323 H H H OEt H Me H H H XVII-324 H H H OCOMe H Me H H H XVII-325 H H H OCOOMe H Me H H H XVII-326 H H H OCONHMe H Me H H H XVII-327 H H H OCONMe₂ H Me H H H XVII-328 H H H OCSMe H Me H H H XVII-329 H H H OCSNMe2 H Me H H H XVII-330 H H H SMe H Me H H H XVII-331 H H H SEt H Me H H H XVII-332 H H H SCOMe H Me H H H XVII-333 H H H SCSNMe₂ H Me H H H XVII-334 H H H SCSNHMe H Me H H H XVII-335 H H H NHMe H Me H H H XVII-336 H H H NH₂ H Me H H H XVII-337 H H H NMe₂ H Me H H H XVII-338 H H H NHCOMe H Me H H H XVII-339 H H H NHCONH₂ H Me H H H XVII-340 H H H NHCONHMe H Me H H H XVII-341 H H H NHCONMe₂ H Me H H H XVII-342 H H H phenyl H Me H H H XVII-343 H H H 2-chloro- H Me H H H phenyl XVII-344 H H H 4- H Me H H H nitrophenyl XVII-345 H H H 2-pyridyl H Me H H H XVII-346 H H H 3-pyridyl H Me H H H XVII-347 H H H 4-pyridyl H Me H H H XVII-348 H H H 2-furyl H Me H H H XVII-349 H H H PhO H Me H H H XVII-350 H Me H Me H Me H H H XVII-351 H Me F Me H Me H H H XVII-352 H Me H F H Me H H H XVII-353 H Me F H H Me H H H XVII-354 H Me Me H H Me H H H XVII-355 H F H Me H Me H H H XVII-356 H F H F H Me H H H XVII-357 Me H H H H F H F H XVII-358 Et H H H H F H F H XVII-359 vinyl H H H H F H F H XVII-360 allyl H H H H F H F H XVII-361 cyclopropyl H H H H F H F H XVII-362 CN H H H H F H F H XVII-363 CONH₂ H H H H F H F H XVII-364 CONHMe H H H H F H F H XVII-365 CONMe₂ H H H H F H F H XVII-366 COMe H H H H F H F H XVII-367 COOH H H H H F H F H XVII-368 COOMe H H H H F H F H XVII-369 CSNHMe H H H H F H F H XVII-370 H Me H H H F H F H XVII-371 H Et H H H F H F H XVII-372 H vinyl H H H F H F H XVII-373 H allyl H H H F H F H XVII-374 H cyclopropyl H H H F H F H XVII-375 H F H H H F H F H XVII-376 H Cl H H H F H F H XVII-377 H NO₂ H H H F H F H XVII-378 H CN H H H F H F H XVII-379 H CONH₂ H H H F H F H XVII-380 H CONHMe H H H F H F H XVII-381 H CONMe₂ H H H F H F H XVII-382 H COMe H H H F H F H XVII-383 H COOH H H H F H F H XVII-384 H COOMe H H H F H F H XVII-385 H CSOMe H H H F H F H XVII-386 H CSNH₂ H H H F H F H XVII-387 H CSNMe₂ H H H F H F H XVII-388 H CSNHMe H H H F H F H XVII-389 H OMe H H H F H F H XVII-390 H OEt H H H F H F H XVII-391 H OCOMe H H H F H F H XVII-392 H OCOOMe H H H F H F H XVII-393 H OCONHMe H H H F H F H XVII-394 H OCONMe₂ H H H F H F H XVII-395 H OCSMe H H H F H F H XVII-396 H OCSNMe2 H H H F H F H XVII-397 H SMe H H H F H F H XVII-398 H SEt H H H F H F H XVII-399 H SCOMe H H H F H F H XVII-400 H SCSNMe₂ H H H F H F H XVII-401 H SCSNHMe H H H F H F H XVII-402 H NHMe H H H F H F H XVII-403 H NH₂ H H H F H F H XVII-404 H NMe₂ H H H F H F H XVII-405 H NHCOMe H H H F H F H XVII-406 H NHCONH₂ H H H F H F H XVII-407 H NHCONHMe H H H F H F H XVII-408 H NHCONMe₂ H H H F H F H XVII-409 H phenyl H H H F H F H XVII-410 H 2-chloro- H H H F H F H phenyl XVII-411 H 4-nitrophenyl H H H F H F H XVII-412 H 2-pyridyl H H H F H F H XVII-413 H 3-pyridyl H H H F H F H XVII-414 H 4-pyridyl H H H F H F H XVII-415 H 2-furyl H H H F H F H XVII-416 H PhO H H H F H F H XVII-417 CH₂ H H H F H F H XVII-418 H H H Me H F H F H XVII-419 H H H Et H F H F H XVII-420 H H H vinyl H F H F H XVII-421 H H H allyl H F H F H XVII-422 H H H cyclopropyl H F H F H XVII-423 H H H F H F H F H XVII-424 H H H Cl H F H F H XVII-425 H H H NO₂ H F H F H XVII-426 H H H CN H F H F H XVII-427 H H H CONH₂ H F H F H XVII-428 H H H CONHMe H F H F H XVII-429 H H H CONMe₂ H F H F H XVII-430 H H H COMe H F H F H XVII-431 H H H COOH H F H F H XVII-432 H H H COOMe H F H F H XVII-433 H H H CSOMe H F H F H XVII-434 H H H CSNH₂ H F H F H XVII-435 H H H CSNMe₂ H F H F H XVII-436 H H H CSNHMe H F H F H XVII-437 H H H OMe H F H F H XVII-438 H H H OEt H F H F H XVII-439 H H H OCOMe H F H F H XVII-440 H H H OCOOMe H F H F H XVII-441 H H H OCONHMe H F H F H XVII-442 H H H OCONMe₂ H F H F H XVII-443 H H H OCSMe H F H F H XVII-444 H H H OCSNMe₂ H F H F H XVII-445 H H H SMe H F H F H XVII-446 H H H SEt H F H F H XVII-447 H H H SCOMe H F H F H XVII-448 H H H SCSNMe₂ H F H F H XVII-449 H H H SCSNHMe H F H F H XVII-450 H H H NHMe H F H F H XVII-451 H H H NH₂ H F H F H XVII-452 H H H NMe₂ H F H F H XVII-453 H H H NHCOMe H F H F H XVII-454 H H H NHCONH₂ H F H F H XVII-455 H H H NHCONHMe H F H F H XVII-456 H H H NHCONMe₂ H F H F H XVII-457 H H H phenyl H F H F H XVII-458 H H H 2-chloro- H F H F H phenyl XVII-459 H H H 4- H F H F H nitrophenyl XVII-460 H H H 2-pyridyl H F H F H XVII-461 H H H 3-pyridyl H F H F H XVII-462 H H H 4-pyridyl H F H F H XVII-463 H H H 2-furyl H F H F H XVII-464 H H H PhO H F H F H XVII-465 H Me H Me H F H F H XVII-466 H Me F Me H F H F H XVII-467 H Me H F H F H F H XVII-468 H Me F H H F H F H XVII-469 H Me Me H H F H F H XVII-470 H F H Me H F H F H XVII-471 H F H F H F H F H XVII-472 H H H H H Me H H H XVII-473 H H H H H Et H H H XVII-474 H H H H H vinyl H H H XVII-475 H H H H H allyl H H H XVII-476 H H H H H cyclopropyl H H H XVII-477 H H H H H F H H H XVII-478 H H H H H Cl H H H XVII-479 H H H H H NO₂ H H H XVII-480 H H H H H CN H H H XVII-481 H H H H H CONH₂ H H H XVII-482 H H H H H CONHMe H H H XVII-483 H H H H H CONMe₂ H H H XVII-484 H H H H H COMe H H H XVII-485 H H H H H COOH H H H XVII-486 H H H H H COOMe H H H XVII-487 H H H H H CSOMe H H H XVII-488 H H H H H CSNH₂ H H H XVII-489 H H H H H CSNMe₂ H H H XVII-490 H H H H H CSNHMe H H H XVII-491 H H H H H OMe H H H XVII-492 H H H H H OEt H H H XVII-493 H H H H H OCOMe H H H XVII-494 H H H H H OCOOMe H H H XVII-495 H H H H H OCONHMe H H H XVII-496 H H H H H OCONMe₂ H H H XVII-497 H H H H H OCSMe H H H XVII-498 H H H H H OCSNMe₂ H H H XVII-499 H H H H H SMe H H H XVII-500 H H H H H SEt H H H XVII-501 H H H H H SCOMe H H H XVII-502 H H H H H SCSNMe₂ H H H XVII-503 H H H H H SCSNHMe H H H XVII-504 H H H H H NHMe H H H XVII-505 H H H H H NH₂ H H H XVII-506 H H H H H NMe₂ H H H XVII-507 H H H H H NHCOMe H H H XVII-508 H H H H H NHCONH₂ H H H XVII-509 H H H H H NHCONHMe H H H XVII-510 H H H H H NHCONMe₂ H H H XVII-511 H H H H H phenyl H H H XVII-512 H H H H H 2- H H H chloro- phenyl XVII-513 H H H H H 4- H H H nitrophenyl XVII-514 H H H H H 2- H H H pyridyl XVII-515 H H H H H 3- H H H pyridyl XVII-516 H H H H H 4- H H H pyridyl XVII-517 H H H H H 2-furyl H H H XVII-518 H H H H H PhO H H H XVII-519 H H H H H H H Me H XVII-520 H H H H H H H Et H XVII-521 H H H H H H H vinyl H XVII-522 H H H H H H H allyl H XVII-523 H H H H H H H cyclopropyl H XVII-524 H H H H H H H F H XVII-525 H H H H H H H Cl H XVII-526 H H H H H H H NO₂ H XVII-527 H H H H H H H CN H XVII-528 H H H H H H H CONH₂ H XVII-529 H H H H H H H CONHMe H XVII-530 H H H H H H H CONMe₂ H XVII-531 H H H H H H H COMe H XVII-532 H H H H H H H COOH H XVII-533 H H H H H H H COOMe H XVII-534 H H H H H H H CSOMe H XVII-535 H H H H H H H CSNH₂ H XVII-536 H H H H H H H CSNMe₂ H XVII-537 H H H H H H H CSNHMe H XVII-538 H H H H H H H OMe H XVII-539 H H H H H H H OEt H XVII-540 H H H H H H H OCOMe H XVII-541 H H H H H H H OCOOMe H XVII-542 H H H H H H H OCONHMe H XVII-543 H H H H H H H OCONMe₂ H XVII-544 H H H H H H H OCSMe H XVII-545 H H H H H H H OCSNMe2 H XVII-546 H H H H H H H SMe H XVII-547 H H H H H H H SEt H XVII-548 H H H H H H H SCOMe H XVII-549 H H H H H H H SCSNMe₂ H XVII-550 H H H H H H H SCSNHMe H XVII-551 H H H H H H H NHMe H XVII-552 H H H H H H H NH₂ H XVII-553 H H H H H H H NMe₂ H XVII-554 H H H H H H H NHCOMe H XVII-555 H H H H H H H NHCONH₂ H XVII-556 H H H H H H H NHCONHMe H XVII-557 H H H H H H H NHCONMe₂ H XVII-558 H H H H H H H phenyl H XVII-559 H H H H H H H 2- H chloro- phenyl XVII-560 H H H H H H H 4- H nitrophenyl XVII-561 H H H H H H H 2- H pyridyl XVII-562 H H H H H H H 3- H pyridyl XVII-563 H H H H H H H 4- H pyridyl XVII-564 H H H H H H H 2-furyl H XVII-565 H H H H H H H PhO H XVII-566 H H H H H H H H Me XVII-567 H H H H H H H H Et XVII-568 H H H H H H H H vinyl XVII-569 H H H H H H H H allyl XVII-570 H H H H H H H H cyclopropyl XVII-571 H H H H H H H H F XVII-572 H H H H H H H H Cl XVII-573 H H H H H H H H NO₂ XVII-574 H H H H H H H H CN XVII-575 H H H H H H H H CONH₂ XVII-576 H H H H H H H H CONHMe XVII-577 H H H H H H H H CONMe₂ XVII-578 H H H H H H H H COMe XVII-579 H H H H H H H H COOH XVII-580 H H H H H H H H COOMe XVII-581 H H H H H H H H CSOMe XVII-582 H H H H H H H H CSNH₂ XVII-583 H H H H H H H H CSNMe₂ XVII-584 H H H H H H H H CSNHMe XVII-585 H H H H H H H H OMe XVII-586 H H H H H H H H OEt XVII-587 H H H H H H H H OCOMe XVII-588 H H H H H H H H OCOOMe XVII-589 H H H H H H H H OCONHMe XVII-590 H H H H H H H H OCONMe₂ XVII-591 H H H H H H H H OCSMe XVII-592 H H H H H H H H OCSNMe2 XVII-593 H H H H H H H H SMe XVII-594 H H H H H H H H SEt XVII-595 H H H H H H H H SCOMe XVII-596 H H H H H H H H SCSNMe₂ XVII-597 H H H H H H H H SCSNHMe XVII-598 H H H H H H H H NHMe XVII-599 H H H H H H H H NH₂ XVII-600 H H H H H H H H NMe₂ XVII-601 H H H H H H H H NHCOMe XVII-602 H H H H H H H H NHCONH₂ XVII-603 H H H H H H H H NHCONHMe XVII-604 H H H H H H H H NHCONMe₂ XVII-605 H H H H H H H H phenyl XVII-606 H H H H H H H H 2- chloro- phenyl XVII-607 H H H H H H H H 4- nitrophenyl XVII-608 H H H H H H H H 2- pyridyl XVII-609 H H H H H H H H 3- pyridyl XVII-610 H H H H H H H H 4- pyridyl XVII-611 H H H H H H H H 2-furyl XVII-612 H H H H H H H H PhO

Table XVIII provides 612 compounds of formula Ir

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4a), R⁵, R⁶ and R⁹ are given in Table 2.

Table XIX provides 612 compounds of formula Is

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XX provides 612 compounds of formula It

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XXI provides 612 compounds of formula Iu

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XXII provides 612 compounds of formula Iv

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XXIII provides 612 compounds of formula Iw

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XXIV provides 612 compounds of formula Ix

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XXV provides 612 compounds of formula Iy

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XXVI provides 612 compounds of formula Iz

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 2.

Table XXVII provides 612 compounds of formula Iaa

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 3.

TABLE 3 Compound No R9 R1 R2 R5 R6 R4a R4b R4c R4d XXVII-1 Me H H H H H H H H XXVII-2 Et H H H H H H H H XXVII-3 vinyl H H H H H H H H XXVII-4 allyl H H H H H H H H XXVII-5 cyclopropyl H H H H H H H H XXVII-6 CN H H H H H H H H XXVII-7 CONH₂ H H H H H H H H XXVII-8 CONHMe H H H H H H H H XXVII-9 CONMe₂ H H H H H H H H XXVII-10 COMe H H H H H H H H XXVII-11 COOH H H H H H H H H XXVII-12 COOMe H H H H H H H H XXVII-13 CSNHMe H H H H H H H H XXVII-14 H Me H H H H H H H XXVII-15 H Et H H H H H H H XXVII-16 H vinyl H H H H H H H XXVII-17 H allyl H H H H H H H XXVII-18 H cyclopropyl H H H H H H H XXVII-19 H F H H H H H H H XXVII-20 H Cl H H H H H H H XXVII-21 H NO₂ H H H H H H H XXVII-22 H CN H H H H H H H XXVII-23 H CONH₂ H H H H H H H XXVII-24 H CONHMe H H H H H H H XXVII-25 H CONMe₂ H H H H H H H XXVII-26 H COMe H H H H H H H XXVII-27 H COOH H H H H H H H XXVII-28 H COOMe H H H H H H H XXVII-29 H CSOMe H H H H H H H XXVII-30 H CSNH₂ H H H H H H H XXVII-31 H CSNMe₂ H H H H H H H XXVII-32 H CSNHMe H H H H H H H XXVII-33 H OMe H H H H H H H XXVII-34 H OEt H H H H H H H XXVII-35 H OCOMe H H H H H H H XXVII-36 H OCOOMe H H H H H H H XXVII-37 H OCONHMe H H H H H H H XXVII-38 H OCONMe₂ H H H H H H H XXVII-39 H OCSMe H H H H H H H XXVII-40 H OCSNMe2 H H H H H H H XXVII-41 H SMe H H H H H H H XXVII-42 H SEt H H H H H H H XXVII-43 H SCOMe H H H H H H H XXVII-44 H SCSNMe₂ H H H H H H H XXVII-45 H SCSNHMe H H H H H H H XXVII-46 H NHMe H H H H H H H XXVII-47 H NH₂ H H H H H H H XXVII-48 H NMe₂ H H H H H H H XXVII-49 H NHCOMe H H H H H H H XXVII-50 H NHCONH₂ H H H H H H H XXVII-51 H NHCONHMe H H H H H H H XXVII-52 H NHCONMe₂ H H H H H H H XXVII-53 H phenyl H H H H H H H XXVII-54 H 2- H H H H H H H chloro- phenyl XXVII-55 H 4- H H H H H H H nitrophenyl XXVII-56 H 2- H H H H H H H pyridyl XXVII-57 H 3- H H H H H H H pyridyl XXVII-58 H 4- H H H H H H H pyridyl XXVII-59 H 2-furyl H H H H H H H XXVII-60 H PhO H H H H H H H XXVII-61 CH₂ H H H H H H H XXVII-62 H ═O H H H H H H XXVII-63 H ═NOH H H H H H H XXVII-64 H ═NOMe H H H H H H XXVII-65 H ═CH₂ H H H H H H XXVII-66 H ═CHMe H H H H H H XXVII-67 H H H H H H H H H XXVII-68 H H H Me H H H H H XXVII-69 H H H Et H H H H H XXVII-70 H H H vinyl H H H H H XXVII-71 H H H allyl H H H H H XXVII-72 H H H cyclopropyl H H H H H XXVII-73 H H H F H H H H H XXVII-74 H H H Cl H H H H H XXVII-75 H H H NO₂ H H H H H XXVII-76 H H H CN H H H H H XXVII-77 H H H CONH₂ H H H H H XXVII-78 H H H CONHMe H H H H H XXVII-79 H H H CONMe₂ H H H H H XXVII-80 H H H COMe H H H H H XXVII-81 H H H COOH H H H H H XXVII-82 H H H COOMe H H H H H XXVII-83 H H H CSOMe H H H H H XXVII-84 H H H CSNH₂ H H H H H XXVII-85 H H H CSNMe₂ H H H H H XXVII-86 H H H CSNHMe H H H H H XXVII-87 H H H OMe H H H H H XXVII-88 H H H OEt H H H H H XXVII-89 H H H OCOMe H H H H H XXVII-90 H H H OCOOMe H H H H H XXVII-91 H H H OCONHMe H H H H H XXVII-92 H H H OCONMe₂ H H H H H XXVII-93 H H H OCSMe H H H H H XXVII-94 H H H OCSNMe2 H H H H H XXVII-95 H H H SMe H H H H H XXVII-96 H H H SEt H H H H H XXVII-97 H H H SCOMe H H H H H XXVII-98 H H H SCSNMe₂ H H H H H XXVII-99 H H H SCSNHMe H H H H H XXVII-100 H H H NHMe H H H H H XXVII-101 H H H NH₂ H H H H H XXVII-102 H H H NMe₂ H H H H H XXVII-103 H H H NHCOMe H H H H H XXVII-104 H H H NHCONH₂ H H H H H XXVII-105 H H H NHCONHMe H H H H H XXVII-106 H H H NHCONMe₂ H H H H H XXVII-107 H H H phenyl H H H H H XXVII-108 H H H 2- H H H H H chloro- phenyl XXVII-109 H H H 4- H H H H H nitrophenyl XXVII-110 H H H 2- H H H H H pyridyl XXVII-111 H H H 3- H H H H H pyridyl XXVII-112 H H H 4- H H H H H pyridyl XXVII-113 H H H 2-furyl H H H H H XXVII-114 H H H PhO H H H H H XXVII-115 H H H ═O H H H H XXVII-116 H H H ═NOH H H H H XXVII-117 H H H ═NOMe H H H H XXVII-118 H H H ═CH₂ H H H H XXVII-119 H H H ═CHMe H H H H XXVII-120 H Me H Me H H H H H XXVII-121 H Me F Me H H H H H XXVII-122 H Me H F H H H H H XXVII-123 H Me F H H H H H H XXVII-124 H Me Me H H H H H H XXVII-125 H F H Me H H H H H XXVII-126 H F H F H H H H H XXVII-127 Me H H H H F H H H XXVII-128 Et H H H H F H H H XXVII-129 vinyl H H H H F H H H XXVII-130 allyl H H H H F H H H XXVII-131 cyclopropyl H H H H F H H H XXVII-132 CN H H H H F H H H XXVII-133 CONH₂ H H H H F H H H XXVII-134 CONHMe H H H H F H H H XXVII-135 CONMe₂ H H H H F H H H XXVII-136 COMe H H H H F H H H XXVII-137 COOH H H H H F H H H XXVII-138 COOMe H H H H F H H H XXVII-139 CSNHMe H H H H F H H H XXVII-140 H Me H H H F H H H XXVII-141 H Et H H H F H H H XXVII-142 H vinyl H H H F H H H XXVII-143 H allyl H H H F H H H XXVII-144 H cyclopropyl H H H F H H H XXVII-145 H F H H H F H H H XXVII-146 H Cl H H H F H H H XXVII-147 H NO₂ H H H F H H H XXVII-148 H CN H H H F H H H XXVII-149 H CONH₂ H H H F H H H XXVII-150 H CONHMe H H H F H H H XXVII-151 H CONMe₂ H H H F H H H XXVII-152 H COMe H H H F H H H XXVII-153 H COOH H H H F H H H XXVII-154 H COOMe H H H F H H H XXVII-155 H CSOMe H H H F H H H XXVII-156 H CSNH₂ H H H F H H H XXVII-157 H CSNMe₂ H H H F H H H XXVII-158 H CSNHMe H H H F H H H XXVII-159 H OMe H H H F H H H XXVII-160 H OEt H H H F H H H XXVII-161 H OCOMe H H H F H H H XXVII-162 H OCOOMe H H H F H H H XXVII-163 H OCONHMe H H H F H H H XXVII-164 H OCONMe₂ H H H F H H H XXVII-165 H OCSMe H H H F H H H XXVII-166 H OCSNMe2 H H H F H H H XXVII-167 H SMe H H H F H H H XXVII-168 H SEt H H H F H H H XXVII-169 H SCOMe H H H F H H H XXVII-170 H SCSNMe₂ H H H F H H H XXVII-171 H SCSNHMe H H H F H H H XXVII-172 H NHMe H H H F H H H XXVII-173 H NH₂ H H H F H H H XXVII-174 H NMe₂ H H H F H H H XXVII-175 H NHCOMe H H H F H H H XXVII-176 H NHCONH₂ H H H F H H H XXVII-177 H NHCONHMe H H H F H H H XXVII-178 H NHCONMe₂ H H H F H H H XXVII-179 H phenyl H H H F H H H XXVII-180 H 2- H H H F H H H chloro- phenyl XXVII-181 H 4- H H H F H H H nitrophenyl XXVII-182 H 2- H H H F H H H pyridyl XXVII-183 H 3- H H H F H H H pyridyl XXVII-184 H 4- H H H F H H H pyridyl XXVII-185 H 2-furyl H H H F H H H XXVII-186 H PhO H H H F H H H XXVII-187 CH₂ H H H F H H H XXVII-188 H H H Me H F H H H XXVII-189 H H H Et H F H H H XXVII-190 H H H vinyl H F H H H XXVII-191 H H H allyl H F H H H XXVII-192 H H H cyclopropyl H F H H H XXVII-193 H H H F H F H H H XXVII-194 H H H Cl H F H H H XXVII-195 H H H NO₂ H F H H H XXVII-196 H H H CN H F H H H XXVII-197 H H H CONH₂ H F H H H XXVII-198 H H H CONHMe H F H H H XXVII-199 H H H CONMe₂ H F H H H XXVII-200 H H H COMe H F H H H XXVII-201 H H H COOH H F H H H XXVII-202 H H H COOMe H F H H H XXVII-203 H H H CSOMe H F H H H XXVII-204 H H H CSNH₂ H F H H H XXVII-205 H H H CSNMe₂ H F H H H XXVII-206 H H H CSNHMe H F H H H XXVII-207 H H H OMe H F H H H XXVII-208 H H H OEt H F H H H XXVII-209 H H H OCOMe H F H H H XXVII-210 H H H OCOOMe H F H H H XXVII-211 H H H OCONHMe H F H H H XXVII-212 H H H OCONMe₂ H F H H H XXVII-213 H H H OCSMe H F H H H XXVII-214 H H H OCSNMe2 H F H H H XXVII-215 H H H SMe H F H H H XXVII-216 H H H SEt H F H H H XXVII-217 H H H SCOMe H F H H H XXVII-218 H H H SCSNMe₂ H F H H H XXVII-219 H H H SCSNHMe H F H H H XXVII-220 H H H NHMe H F H H H XXVII-221 H H H NH₂ H F H H H XXVII-222 H H H NMe₂ H F H H H XXVII-223 H H H NHCOMe H F H H H XXVII-224 H H H NHCONH₂ H F H H H XXVII-225 H H H NHCONHMe H F H H H XXVII-226 H H H NHCONMe₂ H F H H H XXVII-227 H H H phenyl H F H H H XXVII-228 H H H 2- H F H H H chloro- phenyl XXVII-229 H H H 4- H F H H H nitrophenyl XXVII-230 H H H 2- H F H H H pyridyl XXVII-231 H H H 3- H F H H H pyridyl XXVII-232 H H H 4- H F H H H pyridyl XXVII-233 H H H 2-furyl H F H H H XXVII-234 H H H PhO H F H H H XXVII-235 H Me H Me H F H H H XXVII-236 H Me F Me H F H H H XXVII-237 H Me H F H F H H H XXVII-238 H Me F H H F H H H XXVII-239 H Me Me H H F H H H XXVII-240 H F H Me H F H H H XXVII-241 H F H F H F H H H XXVII-242 Me H H H H Me H H H XXVII-243 Et H H H H Me H H H XXVII-244 vinyl H H H H Me H H H XXVII-245 allyl H H H H Me H H H XXVII-246 cyclopropyl H H H H Me H H H XXVII-247 CN H H H H Me H H H XXVII-248 CONH₂ H H H H Me H H H XXVII-249 CONHMe H H H H Me H H H XXVII-250 CONMe₂ H H H H Me H H H XXVII-251 COMe H H H H Me H H H XXVII-252 COOH H H H H Me H H H XXVII-253 COOMe H H H H Me H H H XXVII-254 CSNHMe H H H H Me H H H XXVII-255 H Me H H H Me H H H XXVII-256 H Et H H H Me H H H XXVII-257 H vinyl H H H Me H H H XXVII-258 H allyl H H H Me H H H XXVII-259 H cyclopropyl H H H Me H H H XXVII-260 H F H H H Me H H H XXVII-261 H Cl H H H Me H H H XXVII-262 H NO₂ H H H Me H H H XXVII-263 H CN H H H Me H H H XXVII-264 H CONH₂ H H H Me H H H XXVII-265 H CONHMe H H H Me H H H XXVII-266 H CONMe₂ H H H Me H H H XXVII-267 H COMe H H H Me H H H XXVII-268 H COOH H H H Me H H H XXVII-269 H COOMe H H H Me H H H XXVII-270 H CSOMe H H H Me H H H XXVII-271 H CSNH₂ H H H Me H H H XXVII-272 H CSNMe₂ H H H Me H H H XXVII-273 H CSNHMe H H H Me H H H XXVII-274 H OMe H H H Me H H H XXVII-275 H OEt H H H Me H H H XXVII-276 H OCOMe H H H Me H H H XXVII-277 H OCOOMe H H H Me H H H XXVII-278 H OCONHMe H H H Me H H H XXVII-279 H OCONMe₂ H H H Me H H H XXVII-280 H OCSMe H H H Me H H H XXVII-281 H OCSNMe₂ H H H Me H H H XXVII-282 H SMe H H H Me H H H XXVII-283 H SEt H H H Me H H H XXVII-284 H SCOMe H H H Me H H H XXVII-285 H SCSNMe₂ H H H Me H H H XXVII-286 H SCSNHMe H H H Me H H H XXVII-287 H NHMe H H H Me H H H XXVII-288 H NH₂ H H H Me H H H XXVII-289 H NMe₂ H H H Me H H H XXVII-290 H NHCOMe H H H Me H H H XXVII-291 H NHCONH₂ H H H Me H H H XXVII-292 H NHCONHMe H H H Me H H H XXVII-293 H NHCONMe₂ H H H Me H H H XXVII-294 H phenyl H H H Me H H H XXVII-295 H 2- H H H Me H H H chloro- phenyl XXVII-296 H 4- H H H Me H H H nitrophenyl XXVII-297 H 2- H H H Me H H H pyridyl XXVII-298 H 3- H H H Me H H H pyridyl XXVII-299 H 4- H H H Me H H H pyridyl XXVII-300 H 2-furyl H H H Me H H H XXVII-301 H PhO H H H Me H H H XXVII-302 CH₂ H H H Me H H H XXVII-303 H H H Me H Me H H H XXVII-304 H H H Et H Me H H H XXVII-305 H H H vinyl H Me H H H XXVII-306 H H H allyl H Me H H H XXVII-307 H H H cyclopropyl H Me H H H XXVII-308 H H H F H Me H H H XXVII-309 H H H Cl H Me H H H XXVII-310 H H H NO₂ H Me H H H XXVII-311 H H H CN H Me H H H XXVII-312 H H H CONH₂ H Me H H H XXVII-313 H H H CONHMe H Me H H H XXVII-314 H H H CONMe₂ H Me H H H XXVII-315 H H H COMe H Me H H H XXVII-316 H H H COOH H Me H H H XXVII-317 H H H COOMe H Me H H H XXVII-318 H H H CSOMe H Me H H H XXVII-319 H H H CSNH₂ H Me H H H XXVII-320 H H H CSNMe₂ H Me H H H XXVII-321 H H H CSNHMe H Me H H H XXVII-322 H H H OMe H Me H H H XXVII-323 H H H OEt H Me H H H XXVII-324 H H H OCOMe H Me H H H XXVII-325 H H H OCOOMe H Me H H H XXVII-326 H H H OCONHMe H Me H H H XXVII-327 H H H OCONMe₂ H Me H H H XXVII-328 H H H OCSMe H Me H H H XXVII-329 H H H OCSNMe₂ H Me H H H XXVII-330 H H H SMe H Me H H H XXVII-331 H H H SEt H Me H H H XXVII-332 H H H SCOMe H Me H H H XXVII-333 H H H SCSNMe₂ H Me H H H XXVII-334 H H H SCSNHMe H Me H H H XXVII-335 H H H NHMe H Me H H H XXVII-336 H H H NH₂ H Me H H H XXVII-337 H H H NMe₂ H Me H H H XXVII-338 H H H NHCOMe H Me H H H XXVII-339 H H H NHCONH₂ H Me H H H XXVII-340 H H H NHCONHMe H Me H H H XXVII-341 H H H NHCONMe₂ H Me H H H XXVII-342 H H H phenyl H Me H H H XXVII-343 H H H 2- H Me H H H chloro- phenyl XXVII-344 H H H 4- H Me H H H nitrophenyl XXVII-345 H H H 2- H Me H H H pyridyl XXVII-346 H H H 3- H Me H H H pyridyl XXVII-347 H H H 4- H Me H H H pyridyl XXVII-348 H H H 2-furyl H Me H H H XXVII-349 H H H PhO H Me H H H XXVII-350 H Me H Me H Me H H H XXVII-351 H Me F Me H Me H H H XXVII-352 H Me H F H Me H H H XXVII-353 H Me F H H Me H H H XXVII-354 H Me Me H H Me H H H XXVII-355 H F H Me H Me H H H XXVII-356 H F H F H Me H H H XXVII-357 Me H H H H F H F H XXVII-358 Et H H H H F H F H XXVII-359 vinyl H H H H F H F H XXVII-360 allyl H H H H F H F H XXVII-361 cyclopropyl H H H H F H F H XXVII-362 CN H H H H F H F H XXVII-363 CONH₂ H H H H F H F H XXVII-364 CONHMe H H H H F H F H XXVII-365 CONMe₂ H H H H F H F H XXVII-366 COMe H H H H F H F H XXVII-367 COOH H H H H F H F H XXVII-368 COOMe H H H H F H F H XXVII-369 CSNHMe H H H H F H F H XXVII-370 H Me H H H F H F H XXVII-371 H Et H H H F H F H XXVII-372 H vinyl H H H F H F H XXVII-373 H allyl H H H F H F H XXVII-374 H cyclopropyl H H H F H F H XXVII-375 H F H H H F H F H XXVII-376 H Cl H H H F H F H XXVII-377 H NO₂ H H H F H F H XXVII-378 H CN H H H F H F H XXVII-379 H CONH₂ H H H F H F H XXVII-380 H CONHMe H H H F H F H XXVII-381 H CONMe₂ H H H F H F H XXVII-382 H COMe H H H F H F H XXVII-383 H COOH H H H F H F H XXVII-384 H COOMe H H H F H F H XXVII-385 H CSOMe H H H F H F H XXVII-386 H CSNH₂ H H H F H F H XXVII-387 H CSNMe₂ H H H F H F H XXVII-388 H CSNHMe H H H F H F H XXVII-389 H OMe H H H F H F H XXVII-390 H OEt H H H F H F H XXVII-391 H OCOMe H H H F H F H XXVII-392 H OCOOMe H H H F H F H XXVII-393 H OCONHMe H H H F H F H XXVII-394 H OCONMe₂ H H H F H F H XXVII-395 H OCSMe H H H F H F H XXVII-396 H OCSNMe₂ H H H F H F H XXVII-397 H SMe H H H F H F H XXVII-398 H SEt H H H F H F H XXVII-399 H SCOMe H H H F H F H XXVII-400 H SCSNMe₂ H H H F H F H XXVII-401 H SCSNHMe H H H F H F H XXVII-402 H NHMe H H H F H F H XXVII-403 H NH₂ H H H F H F H XXVII-404 H NMe₂ H H H F H F H XXVII-405 H NHCOMe H H H F H F H XXVII-406 H NHCONH₂ H H H F H F H XXVII-407 H NHCONHMe H H H F H F H XXVII-408 H NHCONMe₂ H H H F H F H XXVII-409 H phenyl H H H F H F H XXVII-410 H 2- H H H F H F H chloro- phenyl XXVII-411 H 4- H H H F H F H nitrophenyl XXVII-412 H 2- H H H F H F H pyridyl XXVII-413 H 3- H H H F H F H pyridyl XXVII-414 H 4- H H H F H F H pyridyl XXVII-415 H 2-furyl H H H F H F H XXVII-416 H PhO H H H F H F H XXVII-417 CH₂ H H H F H F H XXVII-418 H H H Me H F H F H XXVII-419 H H H Et H F H F H XXVII-420 H H H vinyl H F H F H XXVII-421 H H H allyl H F H F H XXVII-422 H H H cyclopropyl H F H F H XXVII-423 H H H F H F H F H XXVII-424 H H H Cl H F H F H XXVII-425 H H H NO₂ H F H F H XXVII-426 H H H CN H F H F H XXVII-427 H H H CONH₂ H F H F H XXVII-428 H H H CONHMe H F H F H XXVII-429 H H H CONMe₂ H F H F H XXVII-430 H H H COMe H F H F H XXVII-431 H H H COOH H F H F H XXVII-432 H H H COOMe H F H F H XXVII-433 H H H CSOMe H F H F H XXVII-434 H H H CSNH₂ H F H F H XXVII-435 H H H CSNMe₂ H F H F H XXVII-436 H H H CSNHMe H F H F H XXVII-437 H H H OMe H F H F H XXVII-438 H H H OEt H F H F H XXVII-439 H H H OCOMe H F H F H XXVII-440 H H H OCOOMe H F H F H XXVII-441 H H H OCONHMe H F H F H XXVII-442 H H H OCONMe₂ H F H F H XXVII-443 H H H OCSMe H F H F H XXVII-444 H H H OCSNMe2 H F H F H XXVII-445 H H H SMe H F H F H XXVII-446 H H H SEt H F H F H XXVII-447 H H H SCOMe H F H F H XXVII-448 H H H SCSNMe₂ H F H F H XXVII-449 H H H SCSNHMe H F H F H XXVII-450 H H H NHMe H F H F H XXVII-451 H H H NH₂ H F H F H XXVII-452 H H H NMe₂ H F H F H XXVII-453 H H H NHCOMe H F H F H XXVII-454 H H H NHCONH₂ H F H F H XXVII-455 H H H NHCONHMe H F H F H XXVII-456 H H H NHCONMe₂ H F H F H XXVII-457 H H H phenyl H F H F H XXVII-458 H H H 2- H F H F H chloro- phenyl XXVII-459 H H H 4- H F H F H nitrophenyl XXVII-460 H H H 2- H F H F H pyridyl XXVII-461 H H H 3- H F H F H pyridyl XXVII-462 H H H 4- H F H F H pyridyl XXVII-463 H H H 2-furyl H F H F H XXVII-464 H H H PhO H F H F H XXVII-465 H Me H Me H F H F H XXVII-466 H Me F Me H F H F H XXVII-467 H Me H F H F H F H XXVII-468 H Me F H H F H F H XXVII-469 H Me Me H H F H F H XXVII-470 H F H Me H F H F H XXVII-471 H F H F H F H F H XXVII-472 H H H H H Me H H H XXVII-473 H H H H H Et H H H XXVII-474 H H H H H vinyl H H H XXVII-475 H H H H H allyl H H H XXVII-476 H H H H H cyclopropyl H H H XXVII-477 H H H H H F H H H XXVII-478 H H H H H Cl H H H XXVII-479 H H H H H NO₂ H H H XXVII-480 H H H H H CN H H H XXVII-481 H H H H H CONH₂ H H H XXVII-482 H H H H H CONHMe H H H XXVII-483 H H H H H CONMe₂ H H H XXVII-484 H H H H H COMe H H H XXVII-485 H H H H H COOH H H H XXVII-486 H H H H H COOMe H H H XXVII-487 H H H H H CSOMe H H H XXVII-488 H H H H H CSNH₂ H H H XXVII-489 H H H H H CSNMe₂ H H H XXVII-490 H H H H H CSNHMe H H H XXVII-491 H H H H H OMe H H H XXVII-492 H H H H H OEt H H H XXVII-493 H H H H H OCOMe H H H XXVII-494 H H H H H OCOOMe H H H XXVII-495 H H H H H OCONHMe H H H XXVII-496 H H H H H OCONMe₂ H H H XXVII-497 H H H H H OCSMe H H H XXVII-498 H H H H H OCSNMe2 H H H XXVII-499 H H H H H SMe H H H XXVII-500 H H H H H SEt H H H XXVII-501 H H H H H SCOMe H H H XXVII-502 H H H H H SCSNMe₂ H H H XXVII-503 H H H H H SCSNHMe H H H XXVII-504 H H H H H NHMe H H H XXVII-505 H H H H H NH₂ H H H XXVII-506 H H H H H NMe₂ H H H XXVII-507 H H H H H NHCOMe H H H XXVII-508 H H H H H NHCONH₂ H H H XXVII-509 H H H H H NHCONHMe H H H XXVII-510 H H H H H NHCONMe₂ H H H XXVII-511 H H H H H phenyl H H H XXVII-512 H H H H H 2- H H H chloro- phenyl XXVII-513 H H H H H 4- H H H nitrophenyl XXVII-514 H H H H H 2- H H H pyridyl XXVII-515 H H H H H 3- H H H pyridyl XXVII-516 H H H H H 4- H H H pyridyl XXVII-517 H H H H H 2-furyl H H H XXVII-518 H H H H H PhO H H H XXVII-519 H H H H H H H Me H XXVII-520 H H H H H H H Et H XXVII-521 H H H H H H H vinyl H XXVII-522 H H H H H H H allyl H XXVII-523 H H H H H H H cyclopropyl H XXVII-524 H H H H H H H F H XXVII-525 H H H H H H H Cl H XXVII-526 H H H H H H H NO₂ H XXVII-527 H H H H H H H CN H XXVII-528 H H H H H H H CONH₂ H XXVII-529 H H H H H H H CONHMe H XXVII-530 H H H H H H H CONMe₂ H XXVII-531 H H H H H H H COMe H XXVII-532 H H H H H H H COOH H XXVII-533 H H H H H H H COOMe H XXVII-534 H H H H H H H CSOMe H XXVII-535 H H H H H H H CSNH₂ H XXVII-536 H H H H H H H CSNMe₂ H XXVII-537 H H H H H H H CSNHMe H XXVII-538 H H H H H H H OMe H XXVII-539 H H H H H H H OEt H XXVII-540 H H H H H H H OCOMe H XXVII-541 H H H H H H H OCOOMe H XXVII-542 H H H H H H H OCONHMe H XXVII-543 H H H H H H H OCONMe₂ H XXVII-544 H H H H H H H OCSMe H XXVII-545 H H H H H H H OCSNMe2 H XXVII-546 H H H H H H H SMe H XXVII-547 H H H H H H H SEt H XXVII-548 H H H H H H H SCOMe H XXVII-549 H H H H H H H SCSNMe₂ H XXVII-550 H H H H H H H SCSNHMe H XXVII-551 H H H H H H H NHMe H XXVII-552 H H H H H H H NH₂ H XXVII-553 H H H H H H H NMe₂ H XXVII-554 H H H H H H H NHCOMe H XXVII-555 H H H H H H H NHCONH₂ H XXVII-556 H H H H H H H NHCONHMe H XXVII-557 H H H H H H H NHCONMe₂ H XXVII-558 H H H H H H H phenyl H XXVII-559 H H H H H H H 2-chloro-phenyl H XXVII-560 H H H H H H H 4-nitrophenyl H XXVII-561 H H H H H H H 2-pyridyl H XXVII-562 H H H H H H H 3-pyridyl H XXVII-563 H H H H H H H 4-pyridyl H XXVII-564 H H H H H H H 2-furyl H XXVII-565 H H H H H H H PhO H XXVII-566 H H H H H H H H Me XXVII-567 H H H H H H H H Et XXVII-568 H H H H H H H H vinyl XXVII-569 H H H H H H H H allyl XXVII-570 H H H H H H H H cyclopropyl XXVII-571 H H H H H H H H F XXVII-572 H H H H H H H H Cl XXVII-573 H H H H H H H H NO₂ XXVII-574 H H H H H H H H CN XXVII-575 H H H H H H H H CONH₂ XXVII-576 H H H H H H H H CONHMe XXVII-577 H H H H H H H H CONMe₂ XXVII-578 H H H H H H H H COMe XXVII-579 H H H H H H H H COOH XXVII-580 H H H H H H H H COOMe XXVII-581 H H H H H H H H CSOMe XXVII-582 H H H H H H H H CSNH₂ XXVII-583 H H H H H H H H CSNMe₂ XXVII-584 H H H H H H H H CSNHMe XXVII-585 H H H H H H H H OMe XXVII-586 H H H H H H H H OEt XXVII-587 H H H H H H H H OCOMe XXVII-588 H H H H H H H H OCOOMe XXVII-589 H H H H H H H H OCONHMe XXVII-590 H H H H H H H H OCONMe₂ XXVII-591 H H H H H H H H OCSMe XXVII-592 H H H H H H H H OCSNMe₂ XXVII-593 H H H H H H H H SMe XXVII-594 H H H H H H H H SEt XXVII-595 H H H H H H H H SCOMe XXVII-596 H H H H H H H H SCSNMe₂ XXVII-597 H H H H H H H H SCSNHMe XXVII-598 H H H H H H H H NHMe XXVII-599 H H H H H H H H NH₂ XXVII-600 H H H H H H H H NMe₂ XXVII-601 H H H H H H H H NHCOMe XXVII-602 H H H H H H H H NHCONH₂ XXVII-603 H H H H H H H H NHCONHMe XXVII-604 H H H H H H H H NHCONMe₂ XXVII-605 H H H H H H H H phenyl XXVII-606 H H H H H H H H 2-chloro- phenyl XXVII-607 H H H H H H H H 4- nitrophenyl XXVII-608 H H H H H H H H 2-pyridyl XXVII-609 H H H H H H H H 3-pyridyl XXVII-610 H H H H H H H H 4-pyridyl XXVII-611 H H H H H H H H 2-furyl XXVII-612 H H H H H H H H PhO

Table XXVIII provides 422 compounds of formula Iab

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4

TABLE 4 Compound No R9 R1 R2 R4a R4b R4c R4d XXVIII-1 Me H H H H H H XXVIII-2 Et H H H H H H XXVIII-3 vinyl H H H H H H XXVIII-4 allyl H H H H H H XXVIII-5 cyclopropyl H H H H H H XXVIII-6 CN H H H H H H XXVIII-7 CONH₂ H H H H H H XXVIII-8 CONHMe H H H H H H XXVIII-9 CONMe₂ H H H H H H XXVIII-10 COMe H H H H H H XXVIII-11 COOH H H H H H H XXVIII-12 COOMe H H H H H H XXVIII-13 CSNHMe H H H H H H XXVIII-14 H Me H H H H H XXVIII-15 H Et H H H H H XXVIII-16 H Vinyl H H H H H XXVIII-17 H Allyl H H H H H XXVIII-18 H Cyclopropyl H H H H H XXVIII-19 H F H H H H H XXVIII-20 H Cl H H H H H XXVIII-21 H NO₂ H H H H H XXVIII-22 H CN H H H H H XXVIII-23 H CONH₂ H H H H H XXVIII-24 H CONHMe H H H H H XXVIII-25 H CONMe₂ H H H H H XXVIII-26 H COMe H H H H H XXVIII-27 H COOH H H H H H XXVIII-28 H COOMe H H H H H XXVIII-29 H CSOMe H H H H H XXVIII-30 H CSNH₂ H H H H H XXVIII-31 H CSNMe₂ H H H H H XXVIII-32 H CSNHMe H H H H H XXVIII-33 H OMe H H H H H XXVIII-34 H OEt H H H H H XXVIII-35 H OCOMe H H H H H XXVIII-36 H OCOOMe H H H H H XXVIII-37 H OCONHMe H H H H H XXVIII-38 H OCONMe₂ H H H H H XXVIII-39 H OCSMe H H H H H XXVIII-40 H OCSNMe₂ H H H H H XXVIII-41 H SMe H H H H H XXVIII-42 H SEt H H H H H XXVIII-43 H SCOMe H H H H H XXVIII-44 H SCSNMe₂ H H H H H XXVIII-45 H SCSNHMe H H H H H XXVIII-46 H NHMe H H H H H XXVIII-47 H NH₂ H H H H H XXVIII-48 H NMe₂ H H H H H XXVIII-49 H NHCOMe H H H H H XXVIII-50 H NHCONH₂ H H H H H XXVIII-51 H NHCONHMe H H H H H XXVIII-52 H NHCONMe₂ H H H H H XXVIII-53 H Phenyl H H H H H XXVIII-54 H 2-chloro- H H H H H phenyl XXVIII-55 H 4-nitrophenyl H H H H H XXVIII-56 H 2-pyridyl H H H H H XXVIII-57 H 3-pyridyl H H H H H XXVIII-58 H 4-pyridyl H H H H H XXVIII-59 H 2-furyl H H H H H XXVIII-60 H PhO H H H H H XXVIII-61 CH₂ H H H H H XXVIII-62 H ═O H H H H XXVIII-63 H ═NOH H H H H XXVIII-64 H ═NOMe H H H H XXVIII-65 H ═CH₂ H H H H XXVIII-66 H ═CHMe H H H H XXVIII-67 H H H H H H H XXVIII-68 H Me H H H H H XXVIII-69 H Me F H H H H XXVIII-70 H Et H H H H H XXVIII-71 H Me Me H H H H XXVIII-72 Me H Me H H H H XXVIII-73 H F H H H H H XXVIII-74 Me F H H H H H XXVIII-75 Me H H F H H H XXVIII-76 Et H H F H H H XXVIII-77 vinyl H H F H H H XXVIII-78 allyl H H F H H H XXVIII-79 cyclopropyl H H F H H H XXVIII-80 CN H H F H H H XXVIII-81 CONH₂ H H F H H H XXVIII-82 CONHMe H H F H H H XXVIII-83 CONMe₂ H H F H H H XXVIII-84 COMe H H F H H H XXVIII-85 COOH H H F H H H XXVIII-86 COOMe H H F H H H XXVIII-87 CSNHMe H H F H H H XXVIII-88 H Me H F H H H XXVIII-89 H Et H F H H H XXVIII-90 H vinyl H F H H H XXVIII-91 H allyl H F H H H XXVIII-92 H cyclopropyl H F H H H XXVIII-93 H F H F H H H XXVIII-94 H Cl H F H H H XXVIII-95 H NO₂ H F H H H XXVIII-96 H CN H F H H H XXVIII-97 H CONH₂ H F H H H XXVIII-98 H CONHMe H F H H H XXVIII-99 H CONMe₂ H F H H H XXVIII-100 H COMe H F H H H XXVIII-101 H COOH H F H H H XXVIII-102 H COOMe H F H H H XXVIII-103 H CSOMe H F H H H XXVIII-104 H CSNH₂ H F H H H XXVIII-105 H CSNMe₂ H F H H H XXVIII-106 H CSNHMe H F H H H XXVIII-107 H OMe H F H H H XXVIII-108 H OEt H F H H H XXVIII-109 H OCOMe H F H H H XXVIII-110 H OCOOMe H F H H H XXVIII-111 H OCONHMe H F H H H XXVIII-112 H OCONMe₂ H F H H H XXVIII-113 H OCSMe H F H H H XXVIII-114 H OCSNMe₂ H F H H H XXVIII-115 H SMe H F H H H XXVIII-116 H SEt H F H H H XXVIII-117 H SCOMe H F H H H XXVIII-118 H SCSNMe₂ H F H H H XXVIII-119 H SCSNHMe H F H H H XXVIII-120 H NHMe H F H H H XXVIII-121 H NH₂ H F H H H XXVIII-122 H NMe₂ H F H H H XXVIII-123 H NHCOMe H F H H H XXVIII-124 H NHCONH₂ H F H H H XXVIII-125 H NHCONHMe H F H H H XXVIII-126 H NHCONMe₂ H F H H H XXVIII-127 H phenyl H F H H H XXVIII-128 H 2-chloro- H F H H H phenyl XXVIII-129 H 4-nitrophenyl H F H H H XXVIII-130 H 2-pyridyl H F H H H XXVIII-131 H 3-pyridyl H F H H H XXVIII-132 H 4-pyridyl H F H H H XXVIII-133 H 2-furyl H F H H H XXVIII-134 H PhO H F H H H XXVIII-135 CH₂ H F H H H XXVIII-136 H H H F H H H XXVIII-137 H Me H F H H H XXVIII-138 H Me F F H H H XXVIII-139 H Et H F H H H XXVIII-140 H Me Me F H H H XXVIII-141 Me H Me F H H H XXVIII-142 H F H F H H H XXVIII-143 Me F H F H H H XXVIII-144 Me H H Me H H H XXVIII-145 Et H H Me H H H XXVIII-146 vinyl H H Me H H H XXVIII-147 allyl H H Me H H H XXVIII-148 cyclopropyl H H Me H H H XXVIII-149 CN H H Me H H H XXVIII-150 CONH₂ H H Me H H H XXVIII-151 CONHMe H H Me H H H XXVIII-152 CONMe₂ H H Me H H H XXVIII-153 COMe H H Me H H H XXVIII-154 COOH H H Me H H H XXVIII-155 COOMe H H Me H H H XXVIII-156 CSNHMe H H Me H H H XXVIII-157 H Me H Me H H H XXVIII-158 H Et H Me H H H XXVIII-159 H vinyl H Me H H H XXVIII-160 H allyl H Me H H H XXVIII-161 H cyclopropyl H Me H H H XXVIII-162 H F H Me H H H XXVIII-163 H Cl H Me H H H XXVIII-164 H NO₂ H Me H H H XXVIII-165 H CN H Me H H H XXVIII-166 H CONH₂ H Me H H H XXVIII-167 H CONHMe H Me H H H XXVIII-168 H CONMe₂ H Me H H H XXVIII-169 H COMe H Me H H H XXVIII-170 H COOH H Me H H H XXVIII-171 H COOMe H Me H H H XXVIII-172 H CSOMe H Me H H H XXVIII-173 H CSNH₂ H Me H H H XXVIII-174 H CSNMe₂ H Me H H H XXVIII-175 H CSNHMe H Me H H H XXVIII-176 H OMe H Me H H H XXVIII-177 H OEt H Me H H H XXVIII-178 H OCOMe H Me H H H XXVIII-179 H OCOOMe H Me H H H XXVIII-180 H OCONHMe H Me H H H XXVIII-181 H OCONMe₂ H Me H H H XXVIII-182 H OCSMe H Me H H H XXVIII-183 H OCSNMe₂ H Me H H H XXVIII-184 H SMe H Me H H H XXVIII-185 H SEt H Me H H H XXVIII-186 H SCOMe H Me H H H XXVIII-187 H SCSNMe₂ H Me H H H XXVIII-188 H SCSNHMe H Me H H H XXVIII-189 H NHMe H Me H H H XXVIII-190 H NH₂ H Me H H H XXVIII-191 H NMe₂ H Me H H H XXVIII-192 H NHCOMe H Me H H H XXVIII-193 H NHCONH₂ H Me H H H XXVIII-194 H NHCONHMe H Me H H H XXVIII-195 H NHCONMe₂ H Me H H H XXVIII-196 H phenyl H Me H H H XXVIII-197 H 2-chloro- H Me H H H phenyl XXVIII-198 H 4-nitrophenyl H Me H H H XXVIII-199 H 2-pyridyl H Me H H H XXVIII-200 H 3-pyridyl H Me H H H XXVIII-201 H 4-pyridyl H Me H H H XXVIII-202 H 2-furyl H Me H H H XXVIII-203 H PhO H Me H H H XXVIII-204 CH₂ H Me H H H XXVIII-205 H H H Me H H H XXVIII-206 H Me H Me H H H XXVIII-207 H Me F Me H H H XXVIII-208 H Et H Me H H H XXVIII-209 H Me Me Me H H H XXVIII-210 Me H Me Me H H H XXVIII-211 H F H Me H H H XXVIII-212 Me F H Me H H H XXVIII-213 Me H H F H F H XXVIII-214 Et H H F H F H XXVIII-215 vinyl H H F H F H XXVIII-216 allyl H H F H F H XXVIII-217 cyclopropyl H H F H F H XXVIII-218 CN H H F H F H XXVIII-219 CONH₂ H H F H F H XXVIII-220 CONHMe H H F H F H XXVIII-221 CONMe₂ H H F H F H XXVIII-222 COMe H H F H F H XXVIII-223 COOH H H F H F H XXVIII-224 COOMe H H F H F H XXVIII-225 CSNHMe H H F H F H XXVIII-226 H Me H F H F H XXVIII-227 H Et H F H F H XXVIII-228 H vinyl H F H F H XXVIII-229 H allyl H F H F H XXVIII-230 H cyclopropyl H F H F H XXVIII-231 H F H F H F H XXVIII-232 H Cl H F H F H XXVIII-233 H NO₂ H F H F H XXVIII-234 H CN H F H F H XXVIII-235 H CONH₂ H F H F H XXVIII-236 H CONHMe H F H F H XXVIII-237 H CONMe₂ H F H F H XXVIII-238 H COMe H F H F H XXVIII-239 H COOH H F H F H XXVIII-240 H COOMe H F H F H XXVIII-241 H CSOMe H F H F H XXVIII-242 H CSNH₂ H F H F H XXVIII-243 H CSNMe₂ H F H F H XXVIII-244 H CSNHMe H F H F H XXVIII-245 H OMe H F H F H XXVIII-246 H OEt H F H F H XXVIII-247 H OCOMe H F H F H XXVIII-248 H OCOOMe H F H F H XXVIII-249 H OCONHMe H F H F H XXVIII-250 H OCONMe₂ H F H F H XXVIII-251 H OCSMe H F H F H XXVIII-252 H OCSNMe₂ H F H F H XXVIII-253 H SMe H F H F H XXVIII-254 H SEt H F H F H XXVIII-255 H SCOMe H F H F H XXVIII-256 H SCSNMe₂ H F H F H XXVIII-257 H SCSNHMe H F H F H XXVIII-258 H NHMe H F H F H XXVIII-259 H NH₂ H F H F H XXVIII-260 H NMe₂ H F H F H XXVIII-261 H NHCOMe H F H F H XXVIII-262 H NHCONH₂ H F H F H XXVIII-263 H NHCONHMe H F H F H XXVIII-264 H NHCONMe₂ H F H F H XXVIII-265 H phenyl H F H F H XXVIII-266 H 2-chloro- H F H F H phenyl XXVIII-267 H 4-nitrophenyl H F H F H XXVIII-268 H 2-pyridyl H F H F H XXVIII-269 H 3-pyridyl H F H F H XXVIII-270 H 4-pyridyl H F H F H XXVIII-271 H 2-furyl H F H F H XXVIII-272 H PhO H F H F H XXVIII-273 CH₂ H F H F H XXVIII-274 H H H F H F H XXVIII-275 H Me H F H F H XXVIII-276 H Me F F H F H XXVIII-277 H Et H F H F H XXVIII-278 H Me Me F H F H XXVIII-279 Me H Me F H F H XXVIII-280 H F H F H F H XXVIII-281 Me F H F H F H XXVIII-282 H H H Me H H H XXVIII-283 H H H Et H H H XXVIII-284 H H H vinyl H H H XXVIII-285 H H H allyl H H H XXVIII-286 H H H cyclopropyl H H H XXVIII-287 H H H F H H H XXVIII-288 H H H Cl H H H XXVIII-289 H H H NO₂ H H H XXVIII-290 H H H CN H H H XXVIII-291 H H H CONH₂ H H H XXVIII-292 H H H CONHMe H H H XXVIII-293 H H H CONMe₂ H H H XXVIII-294 H H H COMe H H H XXVIII-295 H H H COOH H H H XXVIII-296 H H H COOMe H H H XXVIII-297 H H H CSOMe H H H XXVIII-298 H H H CSNH₂ H H H XXVIII-299 H H H CSNMe₂ H H H XXVIII-300 H H H CSNHMe H H H XXVIII-301 H H H OMe H H H XXVIII-302 H H H OEt H H H XXVIII-303 H H H OCOMe H H H XXVIII-304 H H H OCOOMe H H H XXVIII-305 H H H OCONHMe H H H XXVIII-306 H H H OCONMe₂ H H H XXVIII-307 H H H OCSMe H H H XXVIII-308 H H H OCSNMe₂ H H H XXVIII-309 H H H SMe H H H XXVIII-310 H H H SEt H H H XXVIII-311 H H H SCOMe H H H XXVIII-312 H H H SCSNMe₂ H H H XXVIII-313 H H H SCSNHMe H H H XXVIII-314 H H H NHMe H H H XXVIII-315 H H H NH₂ H H H XXVIII-316 H H H NMe₂ H H H XXVIII-317 H H H NHCOMe H H H XXVIII-318 H H H NHCONH₂ H H H XXVIII-319 H H H NHCONHMe H H H XXVIII-320 H H H NHCONMe₂ H H H XXVIII-321 H H H phenyl H H H XXVIII-322 H H H 2-chloro- H H H phenyl XXVIII-323 H H H 4-nitrophenyl H H H XXVIII-324 H H H 2-pyridyl H H H XXVIII-325 H H H 3-pyridyl H H H XXVIII-326 H H H 4-pyridyl H H H XXVIII-327 H H H 2-furyl H H H XXVIII-328 H H H PhO H H H XXVIII-329 H H H H H Me H XXVIII-330 H H H H H Et H XXVIII-331 H H H H H vinyl H XXVIII-332 H H H H H allyl H XXVIII-333 H H H H H cyclopropyl H XXVIII-334 H H H H H F H XXVIII-335 H H H H H Cl H XXVIII-336 H H H H H NO₂ H XXVIII-337 H H H H H CN H XXVIII-338 H H H H H CONH₂ H XXVIII-339 H H H H H CONHMe H XXVIII-340 H H H H H CONMe₂ H XXVIII-341 H H H H H COMe H XXVIII-342 H H H H H COOH H XXVIII-343 H H H H H COOMe H XXVIII-344 H H H H H CSOMe H XXVIII-345 H H H H H CSNH₂ H XXVIII-346 H H H H H CSNMe₂ H XXVIII-347 H H H H H CSNHMe H XXVIII-348 H H H H H OMe H XXVIII-349 H H H H H OEt H XXVIII-350 H H H H H OCOMe H XXVIII-351 H H H H H OCOOMe H XXVIII-352 H H H H H OCONHMe H XXVIII-353 H H H H H OCONMe₂ H XXVIII-354 H H H H H OCSMe H XXVIII-355 H H H H H OCSNMe₂ H XXVIII-356 H H H H H SMe H XXVIII-357 H H H H H SEt H XXVIII-358 H H H H H SCOMe H XXVIII-359 H H H H H SCSNMe₂ H XXVIII-360 H H H H H SCSNHMe H XXVIII-361 H H H H H NHMe H XXVIII-362 H H H H H NH₂ H XXVIII-363 H H H H H NMe₂ H XXVIII-364 H H H H H NHCOMe H XXVIII-365 H H H H H NHCONH₂ H XXVIII-366 H H H H H NHCONHMe H XXVIII-367 H H H H H NHCONMe₂ H XXVIII-368 H H H H H phenyl H XXVIII-369 H H H H H 2-chloro- H phenyl XXVIII-370 H H H H H 4-nitrophenyl H XXVIII-371 H H H H H 2-pyridyl H XXVIII-372 H H H H H 3-pyridyl H XXVIII-373 H H H H H 4-pyridyl H XXVIII-374 H H H H H 2-furyl H XXVIII-375 H H H H H PhO H XXVIII-376 H H H H H H Me XXVIII-377 H H H H H H Et XXVIII-378 H H H H H H Vinyl XXVIII-379 H H H H H H Allyl XXVIII-380 H H H H H H Cyclopropyl XXVIII-381 H H H H H H F XXVIII-382 H H H H H H Cl XXVIII-383 H H H H H H NO₂ XXVIII-384 H H H H H H CN XXVIII-385 H H H H H H CONH₂ XXVIII-386 H H H H H H CONHMe XXVIII-387 H H H H H H CONMe₂ XXVIII-388 H H H H H H COMe XXVIII-389 H H H H H H COOH XXVIII-390 H H H H H H COOMe XXVIII-391 H H H H H H CSOMe XXVIII-392 H H H H H H CSNH₂ XXVIII-393 H H H H H H CSNMe₂ XXVIII-394 H H H H H H CSNHMe XXVIII-395 H H H H H H OMe XXVIII-396 H H H H H H OEt XXVIII-397 H H H H H H OCOMe XXVIII-398 H H H H H H OCOOMe XXVIII-399 H H H H H H OCONHMe XXVIII-400 H H H H H H OCONMe₂ XXVIII-401 H H H H H H OCSMe XXVIII-402 H H H H H H OCSNMe₂ XXVIII-403 H H H H H H SMe XXVIII-404 H H H H H H SEt XXVIII-405 H H H H H H SCOMe XXVIII-406 H H H H H H SCSNMe₂ XXVIII-407 H H H H H H SCSNHMe XXVIII-408 H H H H H H NHMe XXVIII-409 H H H H H H NH₂ XXVIII-410 H H H H H H NMe₂ XXVIII-411 H H H H H H NHCOMe XXVIII-412 H H H H H H NHCONH₂ XXVIII-413 H H H H H H NHCONHMe XXVIII-414 H H H H H H NHCONMe₂ XXVIII-415 H H H H H H phenyl XXVIII-416 H H H H H H 2-chloro- phenyl XXVIII-417 H H H H H H 4-nitrophenyl XXVIII-418 H H H H H H 2-pyridyl XXVIII-419 H H H H H H 3-pyridyl XXVIII-420 H H H H H H 4-pyridyl XXVIII-421 H H H H H H 2-furyl XXVIII-422 H H H H H H PhO

Table XXIX provides 422 compounds of formula Iac

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXX provides 422 compounds of formula Iad

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXI provides 422 compounds of formula Iae

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXII provides 422 compounds of formula Iaf

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXIII provides 422 compounds of formula Iag

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXIV provides 422 compounds of formula Iah

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXV provides 422 compounds of formula Iai

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXVI provides 4222 compounds of formula Iaj

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXVII provides 422 compounds of formula Iak

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d) and R⁹ are given in Table 4.

Table XXXVIII provides 391 compounds of formula Ial

wherein the values of Y, R¹, R², T^(a), T^(b), T^(c) and T^(d) are given in Table 5.

TABLE 5 Compound No Y R1 R2 Ta Tb Tc Td XXXVIII-1 CH₂ H H N CH CH CH XXXVIII-2 CHMe H H N CH CH CH XXXVIII-3 CHEt H H N CH CH CH XXXVIII-4 CHF H H N CH CH CH XXXVIII-5 C═CH₂ H H N CH CH CH XXXVIII-6 O H H N CH CH CH XXXVIII-7 S H H N CH CH CH XXXVIII-8 NH H H N CH CH CH XXXVIII-9 NMe H H N CH CH CH XXXVIII-10 NCHO H H N CH CH CH XXXVIII-11 NCOMe H H N CH CH CH XXXVIII-12 CH₂ Me H N CH CH CH XXXVIII-13 O Me H N CH CH CH XXXVIII-14 CHMe Me H N CH CH CH XXXVIII-15 CH₂ ═O N CH CH CH XXXVIII-16 CH₂ ═CH₂ N CH CH CH XXXVIII-17 CH₂ ═CHMe N CH CH CH XXXVIII-18 CH₂ H H N CH CF CH XXXVIII-19 CHMe H H N CH CF CH XXXVIII-20 CHEt H H N CH CF CH XXXVIII-21 CHF H H N CH CF CH XXXVIII-22 C═CH₂ H H N CH CF CH XXXVIII-23 O H H N CH CF CH XXXVIII-24 S H H N CH CF CH XXXVIII-25 NH H H N CH CF CH XXXVIII-26 NMe H H N CH CF CH XXXVIII-27 NCHO H H N CH CF CH XXXVIII-28 NCOMe H H N CH CF CH XXXVIII-29 CH₂ Me H N CH CF CH XXXVIII-30 O Me H N CH CF CH XXXVIII-31 CHMe Me H N CH CF CH XXXVIII-32 CH₂ ═O N CH CF CH XXXVIII-33 CH₂ ═CH₂ N CH CF CH XXXVIII-34 CH₂ ═CHMe N CH CF CH XXXVIII-35 CH₂ H H N CH CH CF XXXVIII-36 CHMe H H N CH CH CF XXXVIII-37 CHEt H H N CH CH CF XXXVIII-38 CHF H H N CH CH CF XXXVIII-39 C═CH₂ H H N CH CH CF XXXVIII-40 O H H N CH CH CF XXXVIII-41 S H H N CH CH CF XXXVIII-42 NH H H N CH CH CF XXXVIII-43 NMe H H N CH CH CF XXXVIII-44 NCHO H H N CH CH CF XXXVIII-45 NCOMe H H N CH CH CF XXXVIII-46 CH₂ Me H N CH CH CF XXXVIII-47 O Me H N CH CH CF XXXVIII-48 CHMe Me H N CH CH CF XXXVIII-49 CH₂ ═O N CH CH CF XXXVIII-50 CH₂ ═CH₂ N CH CH CF XXXVIII-51 CH₂ ═CHMe N CH CH CF XXXVIII-52 CH₂ H H CH N CH CH XXXVIII-53 CHMe H H CH N CH CH XXXVIII-54 CHEt H H CH N CH CH XXXVIII-55 CHF H H CH N CH CH XXXVIII-56 C═CH₂ H H CH N CH CH XXXVIII-57 O H H CH N CH CH XXXVIII-58 S H H CH N CH CH XXXVIII-59 NH H H CH N CH CH XXXVIII-60 NMe H H CH N CH CH XXXVIII-61 NCHO H H CH N CH CH XXXVIII-62 NCOMe H H CH N CH CH XXXVIII-63 CH₂ Me H CH N CH CH XXXVIII-64 O Me H CH N CH CH XXXVIII-65 CHMe Me H CH N CH CH XXXVIII-66 CH₂ ═O CH N CH CH XXXVIII-67 CH₂ ═CH₂ CH N CH CH XXXVIII-68 CH₂ ═CHMe CH N CH CH XXXVIII-69 CH₂ H H CF N CH CH XXXVIII-70 CHMe H H CF N CH CH XXXVIII-71 CHEt H H CF N CH CH XXXVIII-72 CHF H H CF N CH CH XXXVIII-73 C═CH₂ H H CF N CH CH XXXVIII-74 O H H CF N CH CH XXXVIII-75 S H H CF N CH CH XXXVIII-76 NH H H CF N CH CH XXXVIII-77 NMe H H CF N CH CH XXXVIII-78 NCHO H H CF N CH CH XXXVIII-79 NCOMe H H CF N CH CH XXXVIII-80 CH₂ Me H CF N CH CH XXXVIII-81 O Me H CF N CH CH XXXVIII-82 CHMe Me H CF N CH CH XXXVIII-83 CH₂ ═O CF N CH CH XXXVIII-84 CH₂ ═CH₂ CF N CH CH XXXVIII-85 CH₂ ═CHMe CF N CH CH XXXVIII-86 CH₂ H H CMe N CH CH XXXVIII-87 CHMe H H CMe N CH CH XXXVIII-88 CHEt H H CMe N CH CH XXXVIII-89 CHF H H CMe N CH CH XXXVIII-90 C═CH₂ H H CMe N CH CH XXXVIII-91 O H H CMe N CH CH XXXVIII-92 S H H CMe N CH CH XXXVIII-93 NH H H CMe N CH CH XXXVIII-94 NMe H H CMe N CH CH XXXVIII-95 NCHO H H CMe N CH CH XXXVIII-96 NCOMe H H CMe N CH CH XXXVIII-97 CH₂ Me H CMe N CH CH XXXVIII-98 O Me H CMe N CH CH XXXVIII-99 CHMe Me H CMe N CH CH XXXVIII-100 CH₂ ═O CMe N CH CH XXXVIII-101 CH₂ ═CH₂ CMe N CH CH XXXVIII-102 CH₂ ═CHMe CMe N CH CH XXXVIII-103 CH₂ H H CH N CF CH XXXVIII-104 CHMe H H CH N CF CH XXXVIII-105 CHEt H H CH N CF CH XXXVIII-106 CHF H H CH N CF CH XXXVIII-107 C═CH₂ H H CH N CF CH XXXVIII-108 O H H CH N CF CH XXXVIII-109 S H H CH N CF CH XXXVIII-110 NH H H CH N CF CH XXXVIII-111 NMe H H CH N CF CH XXXVIII-112 NCHO H H CH N CF CH XXXVIII-113 NCOMe H H CH N CF CH XXXVIII-114 CH₂ Me H CH N CF CH XXXVIII-115 O Me H CH N CF CH XXXVIII-116 CHMe Me H CH N CF CH XXXVIII-117 CH₂ ═O CH N CF CH XXXVIII-118 CH₂ ═CH₂ CH N CF CH XXXVIII-119 CH₂ ═CHMe CH N CF CH XXXVIII-120 CH₂ H H CH N CH CF XXXVIII-121 CHMe H H CH N CH CF XXXVIII-122 CHEt H H CH N CH CF XXXVIII-123 CHF H H CH N CH CF XXXVIII-124 C═CH₂ H H CH N CH CF XXXVIII-125 O H H CH N CH CF XXXVIII-126 S H H CH N CH CF XXXVIII-127 NH H H CH N CH CF XXXVIII-128 NMe H H CH N CH CF XXXVIII-129 NCHO H H CH N CH CF XXXVIII-130 NCOMe H H CH N CH CF XXXVIII-131 CH₂ Me H CH N CH CF XXXVIII-132 O Me H CH N CH CF XXXVIII-133 CHMe Me H CH N CH CF XXXVIII-134 CH₂ ═O CH N CH CF XXXVIII-135 CH₂ ═CH₂ CH N CH CF XXXVIII-136 CH₂ ═CHMe CH N CH CF XXXVIII-137 CH₂ H H CH CH N CH XXXVIII-138 CHMe H H CH CH N CH XXXVIII-139 CHEt H H CH CH N CH XXXVIII-140 CHF H H CH CH N CH XXXVIII-141 C═CH₂ H H CH CH N CH XXXVIII-142 O H H CH CH N CH XXXVIII-143 S H H CH CH N CH XXXVIII-144 NH H H CH CH N CH XXXVIII-145 NMe H H CH CH N CH XXXVIII-146 NCHO H H CH CH N CH XXXVIII-147 NCOMe H H CH CH N CH XXXVIII-148 CH₂ Me H CH CH N CH XXXVIII-149 O Me H CH CH N CH XXXVIII-150 CHMe Me H CH CH N CH XXXVIII-151 CH₂ ═O CH CH N CH XXXVIII-152 CH₂ ═CH₂ CH CH N CH XXXVIII-153 CH₂ ═CHMe CH CH N CH XXXVIII-154 CH₂ H H CF CH N CH XXXVIII-155 CHMe H H CF CH N CH XXXVIII-156 CHEt H H CF CH N CH XXXVIII-157 CHF H H CF CH N CH XXXVIII-158 C═CH₂ H H CF CH N CH XXXVIII-159 O H H CF CH N CH XXXVIII-160 S H H CF CH N CH XXXVIII-161 NH H H CF CH N CH XXXVIII-162 NMe H H CF CH N CH XXXVIII-163 NCHO H H CF CH N CH XXXVIII-164 NCOMe H H CF CH N CH XXXVIII-165 CH₂ Me H CF CH N CH XXXVIII-166 O Me H CF CH N CH XXXVIII-167 CHMe Me H CF CH N CH XXXVIII-168 CH₂ ═O CF CH N CH XXXVIII-169 CH₂ ═CH₂ CF CH N CH XXXVIII-170 CH₂ ═CHMe CF CH N CH XXXVIII-171 CH₂ H H CMe CH N CH XXXVIII-172 CHMe H H CMe CH N CH XXXVIII-173 CHEt H H CMe CH N CH XXXVIII-174 CHF H H CMe CH N CH XXXVIII-175 C═CH₂ H H CMe CH N CH XXXVIII-176 O H H CMe CH N CH XXXVIII-177 S H H CMe CH N CH XXXVIII-178 NH H H CMe CH N CH XXXVIII-179 NMe H H CMe CH N CH XXXVIII-180 NCHO H H CMe CH N CH XXXVIII-181 NCOMe H H CMe CH N CH XXXVIII-182 CH₂ Me H CMe CH N CH XXXVIII-183 O Me H CMe CH N CH XXXVIII-184 CHMe Me H CMe CH N CH XXXVIII-185 CH₂ ═O CMe CH N CH XXXVIII-186 CH₂ ═CH₂ CMe CH N CH XXXVIII-187 CH₂ ═CHMe CMe CH N CH XXXVIII-188 CH₂ H H CH CH N CF XXXVIII-189 CHMe H H CH CH N CF XXXVIII-190 CHEt H H CH CH N CF XXXVIII-191 CHF H H CH CH N CF XXXVIII-192 C═CH₂ H H CH CH N CF XXXVIII-193 O H H CH CH N CF XXXVIII-194 S H H CH CH N CF XXXVIII-195 NH H H CH CH N CF XXXVIII-196 NMe H H CH CH N CF XXXVIII-197 NCHO H H CH CH N CF XXXVIII-198 NCOMe H H CH CH N CF XXXVIII-199 CH₂ Me H CH CH N CF XXXVIII-200 O Me H CH CH N CF XXXVIII-201 CHMe Me H CH CH N CF XXXVIII-202 CH₂ ═O CH CH N CF XXXVIII-203 CH₂ ═CH₂ CH CH N CF XXXVIII-204 CH₂ ═CHMe CH CH N CF XXXVIII-205 CH₂ H H CH CH CH N XXXVIII-206 CHMe H H CH CH CH N XXXVIII-207 CHEt H H CH CH CH N XXXVIII-208 CHF H H CH CH CH N XXXVIII-209 C═CH₂ H H CH CH CH N XXXVIII-210 O H H CH CH CH N XXXVIII-211 S H H CH CH CH N XXXVIII-212 NH H H CH CH CH N XXXVIII-213 NMe H H CH CH CH N XXXVIII-214 NCHO H H CH CH CH N XXXVIII-215 NCOMe H H CH CH CH N XXXVIII-216 CH₂ Me H CH CH CH N XXXVIII-217 O Me H CH CH CH N XXXVIII-218 CHMe Me H CH CH CH N XXXVIII-219 CH₂ ═O CH CH CH N XXXVIII-220 CH₂ ═CH₂ CH CH CH N XXXVIII-221 CH₂ ═CHMe CH CH CH N XXXVIII-222 CH₂ H H CF CH CH N XXXVIII-223 CHMe H H CF CH CH N XXXVIII-224 CHEt H H CF CH CH N XXXVIII-225 CHF H H CF CH CH N XXXVIII-226 C═CH₂ H H CF CH CH N XXXVIII-227 O H H CF CH CH N XXXVIII-228 S H H CF CH CH N XXXVIII-229 NH H H CF CH CH N XXXVIII-230 NMe H H CF CH CH N XXXVIII-231 NCHO H H CF CH CH N XXXVIII-232 NCOMe H H CF CH CH N XXXVIII-233 CH₂ Me H CF CH CH N XXXVIII-234 O Me H CF CH CH N XXXVIII-235 CHMe Me H CF CH CH N XXXVIII-236 CH₂ ═O CF CH CH N XXXVIII-237 CH₂ ═CH₂ CF CH CH N XXXVIII-238 CH₂ ═CHMe CF CH CH N XXXVIII-239 CH₂ H H CMe CH CH N XXXVIII-240 CHMe H H CMe CH CH N XXXVIII-241 CHEt H H CMe CH CH N XXXVIII-242 CHF H H CMe CH CH N XXXVIII-243 C═CH₂ H H CMe CH CH N XXXVIII-244 O H H CMe CH CH N XXXVIII-245 S H H CMe CH CH N XXXVIII-246 NH H H CMe CH CH N XXXVIII-247 NMe H H CMe CH CH N XXXVIII-248 NCHO H H CMe CH CH N XXXVIII-249 NCOMe H H CMe CH CH N XXXVIII-250 CH₂ Me H CMe CH CH N XXXVIII-251 O Me H CMe CH CH N XXXVIII-252 CHMe Me H CMe CH CH N XXXVIII-253 CH₂ ═O CMe CH CH N XXXVIII-254 CH₂ ═CH₂ CMe CH CH N XXXVIII-255 CH₂ ═CHMe CMe CH CH N XXXVIII-256 CH₂ H H CH CH CF N XXXVIII-257 CHMe H H CH CH CF N XXXVIII-258 CHEt H H CH CH CF N XXXVIII-259 CHF H H CH CH CF N XXXVIII-260 C═CH₂ H H CH CH CF N XXXVIII-261 O H H CH CH CF N XXXVIII-262 S H H CH CH CF N XXXVIII-263 NH H H CH CH CF N XXXVIII-264 NMe H H CH CH CF N XXXVIII-265 NCHO H H CH CH CF N XXXVIII-266 NCOMe H H CH CH CF N XXXVIII-267 CH₂ Me H CH CH CF N XXXVIII-268 O Me H CH CH CF N XXXVIII-269 CHMe Me H CH CH CF N XXXVIII-270 CH₂ ═O CH CH CF N XXXVIII-271 CH₂ ═CH₂ CH CH CF N XXXVIII-272 CH₂ ═CHMe CH CH CF N XXXVIII-273 CH₂ H H N CH N CH XXXVIII-274 CHMe H H N CH N CH XXXVIII-275 CHEt H H N CH N CH XXXVIII-276 CHF H H N CH N CH XXXVIII-277 C═CH₂ H H N CH N CH XXXVIII-278 O H H N CH N CH XXXVIII-279 S H H N CH N CH XXXVIII-280 NH H H N CH N CH XXXVIII-281 NMe H H N CH N CH XXXVIII-282 NCHO H H N CH N CH XXXVIII-283 NCOMe H H N CH N CH XXXVIII-284 CH₂ Me H N CH N CH XXXVIII-285 O Me H N CH N CH XXXVIII-286 CHMe Me H N CH N CH XXXVIII-287 CH₂ ═O N CH N CH XXXVIII-288 CH₂ ═CH₂ N CH N CH XXXVIII-289 CH₂ ═CHMe N CH N CH XXXVIII-290 CH₂ H H N CH N CF XXXVIII-291 CHMe H H N CH N CF XXXVIII-292 CHEt H H N CH N CF XXXVIII-293 CHF H H N CH N CF XXXVIII-294 C═CH₂ H H N CH N CF XXXVIII-295 O H H N CH N CF XXXVIII-296 S H H N CH N CF XXXVIII-297 NH H H N CH N CF XXXVIII-298 NMe H H N CH N CF XXXVIII-299 NCHO H H N CH N CF XXXVIII-300 NCOMe H H N CH N CF XXXVIII-301 CH₂ Me H N CH N CF XXXVIII-302 O Me H N CH N CF XXXVIII-303 CHMe Me H N CH N CF XXXVIII-304 CH₂ ═O N CH N CF XXXVIII-305 CH₂ ═CH₂ N CH N CF XXXVIII-306 CH₂ ═CHMe N CH N CF XXXVIII-307 CH₂ H H N N CH CH XXXVIII-308 CHMe H H N N CH CH XXXVIII-309 CHEt H H N N CH CH XXXVIII-310 CHF H H N N CH CH XXXVIII-311 C═CH₂ H H N N CH CH XXXVIII-312 O H H N N CH CH XXXVIII-313 S H H N N CH CH XXXVIII-314 NH H H N N CH CH XXXVIII-315 NMe H H N N CH CH XXXVIII-316 NCHO H H N N CH CH XXXVIII-317 NCOMe H H N N CH CH XXXVIII-318 CH₂ Me H N N CH CH XXXVIII-319 O Me H N N CH CH XXXVIII-320 CHMe Me H N N CH CH XXXVIII-321 CH₂ ═O N N CH CH XXXVIII-322 CH₂ ═CH₂ N N CH CH XXXVIII-323 CH₂ ═CHMe N N CH CH XXXVIII-324 CH₂ H H N N CF CH XXXVIII-325 CHMe H H N N CF CH XXXVIII-326 CHEt H H N N CF CH XXXVIII-327 CHF H H N N CF CH XXXVIII-328 C═CH₂ H H N N CF CH XXXVIII-329 O H H N N CF CH XXXVIII-330 S H H N N CF CH XXXVIII-331 NH H H N N CF CH XXXVIII-332 NMe H H N N CF CH XXXVIII-333 NCHO H H N N CF CH XXXVIII-334 NCOMe H H N N CF CH XXXVIII-335 CH₂ Me H N N CF CH XXXVIII-336 O Me H N N CF CH XXXVIII-337 CHMe Me H N N CF CH XXXVIII-338 CH₂ ═O N N CF CH XXXVIII-339 CH₂ ═CH₂ N N CF CH XXXVIII-340 CH₂ ═CHMe N N CF CH XXXVIII-341 CH₂ H H N N CH CF XXXVIII-342 CHMe H H N N CH CF XXXVIII-343 CHEt H H N N CH CF XXXVIII-344 CHF H H N N CH CF XXXVIII-345 C═CH₂ H H N N CH CF XXXVIII-346 O H H N N CH CF XXXVIII-347 S H H N N CH CF XXXVIII-348 NH H H N N CH CF XXXVIII-349 NMe H H N N CH CF XXXVIII-350 NCHO H H N N CH CF XXXVIII-351 NCOMe H H N N CH CF XXXVIII-352 CH₂ Me H N N CH CF XXXVIII-353 O Me H N N CH CF XXXVIII-354 CHMe Me H N N CH CF XXXVIII-355 CH₂ ═O N N CH CF XXXVIII-356 CH₂ ═CH₂ N N CH CF XXXVIII-357 CH₂ ═CHMe N N CH CF XXXVIII-358 CH₂ H H N CH CH N XXXVIII-359 CHMe H H N CH CH N XXXVIII-360 CHEt H H N CH CH N XXXVIII-361 CHF H H N CH CH N XXXVIII-362 C═CH₂ H H N CH CH N XXXVIII-363 O H H N CH CH N XXXVIII-364 S H H N CH CH N XXXVIII-365 NH H H N CH CH N XXXVIII-366 NMe H H N CH CH N XXXVIII-367 NCHO H H N CH CH N XXXVIII-368 NCOMe H H N CH CH N XXXVIII-369 CH₂ Me H N CH CH N XXXVIII-370 O Me H N CH CH N XXXVIII-371 CHMe Me H N CH CH N XXXVIII-372 CH₂ ═O N CH CH N XXXVIII-373 CH₂ ═CH₂ N CH CH N XXXVIII-374 CH₂ ═CHMe N CH CH N XXXVIII-375 CH₂ H H CH N CH N XXXVIII-376 CHMe H H CH N CH N XXXVIII-377 CHEt H H CH N CH N XXXVIII-378 CHF H H CH N CH N XXXVIII-379 C═CH₂ H H CH N CH N XXXVIII-380 O H H CH N CH N XXXVIII-381 S H H CH N CH N XXXVIII-382 NH H H CH N CH N XXXVIII-383 NMe H H CH N CH N XXXVIII-384 NCHO H H CH N CH N XXXVIII-385 NCOMe H H CH N CH N XXXVIII-386 CH₂ Me H CH N CH N XXXVIII-387 O Me H CH N CH N XXXVIII-388 CHMe Me H CH N CH N XXXVIII-389 CH₂ ═O CH N CH N XXXVIII-390 CH₂ ═CH₂ CH N CH N XXXVIII-391 CH₂ ═CHMe CH N CH N

Table XXXIX provides 578 compounds of formula Iam

wherein the values of Y, R¹, R², T^(d), T^(e) and T^(f) are given in Table 6.

TABLE 6 Compound No Y R1 R2 Td Te Tf XXXIX-1 CH₂ H H NH CH CH XXXIX-2 CHMe H H NH CH CH XXXIX-3 CHEt H H NH CH CH XXXIX-4 CHF H H NH CH CH XXXIX-5 C═CH₂ H H NH CH CH XXXIX-6 O H H NH CH CH XXXIX-7 S H H NH CH CH XXXIX-8 NH H H NH CH CH XXXIX-9 NMe H H NH CH CH XXXIX-10 NCHO H H NH CH CH XXXIX-11 NCOMe H H NH CH CH XXXIX-12 CH₂ Me H NH CH CH XXXIX-13 O Me H NH CH CH XXXIX-14 CHMe Me H NH CH CH XXXIX-15 CH₂ ═O NH CH CH XXXIX-16 CH₂ ═CH₂ NH CH CH XXXIX-17 CH₂ ═CHMe NH CH CH XXXIX-18 CH₂ H H NH CF CH XXXIX-19 CHMe H H NH CF CH XXXIX-20 CHEt H H NH CF CH XXXIX-21 CHF H H NH CF CH XXXIX-22 C═CH₂ H H NH CF CH XXXIX-23 O H H NH CF CH XXXIX-24 S H H NH CF CH XXXIX-25 NH H H NH CF CH XXXIX-26 NMe H H NH CF CH XXXIX-27 NCHO H H NH CF CH XXXIX-28 NCOMe H H NH CF CH XXXIX-29 CH₂ Me H NH CF CH XXXIX-30 O Me H NH CF CH XXXIX-31 CHMe Me H NH CF CH XXXIX-32 CH₂ ═O NH CF CH XXXIX-33 CH₂ ═CH₂ NH CF CH XXXIX-34 CH₂ ═CHMe NH CF CH XXXIX-35 CH₂ H H NH CMe CH XXXIX-36 CHMe H H NH CMe CH XXXIX-37 CHEt H H NH CMe CH XXXIX-38 CHF H H NH CMe CH XXXIX-39 C═CH₂ H H NH CMe CH XXXIX-40 O H H NH CMe CH XXXIX-41 S H H NH CMe CH XXXIX-42 NH H H NH CMe CH XXXIX-43 NMe H H NH CMe CH XXXIX-44 NCHO H H NH CMe CH XXXIX-45 NCOMe H H NH CMe CH XXXIX-46 CH₂ Me H NH CMe CH XXXIX-47 O Me H NH CMe CH XXXIX-48 CHMe Me H NH CMe CH XXXIX-49 CH₂ ═O NH CMe CH XXXIX-50 CH₂ ═CH₂ NH CMe CH XXXIX-51 CH₂ ═CHMe NH CMe CH XXXIX-52 CH₂ H H NH CH CMe XXXIX-53 CHMe H H NH CH CMe XXXIX-54 CHEt H H NH CH CMe XXXIX-55 CHF H H NH CH CMe XXXIX-56 C═CH₂ H H NH CH CMe XXXIX-57 O H H NH CH CMe XXXIX-58 S H H NH CH CMe XXXIX-59 NH H H NH CH CMe XXXIX-60 NMe H H NH CH CMe XXXIX-61 NCHO H H NH CH CMe XXXIX-62 NCOMe H H NH CH CMe XXXIX-63 CH₂ Me H NH CH CMe XXXIX-64 O Me H NH CH CMe XXXIX-65 CHMe Me H NH CH CMe XXXIX-66 CH₂ ═O NH CH CMe XXXIX-67 CH₂ ═CH₂ NH CH CMe XXXIX-68 CH₂ ═CHMe NH CH CMe XXXIX-69 CH₂ H H NMe CH CH XXXIX-70 CHMe H H NMe CH CH XXXIX-71 CHEt H H NMe CH CH XXXIX-72 CHF H H NMe CH CH XXXIX-73 C═CH₂ H H NMe CH CH XXXIX-74 O H H NMe CH CH XXXIX-75 S H H NMe CH CH XXXIX-76 NH H H NMe CH CH XXXIX-77 NMe H H NMe CH CH XXXIX-78 NCHO H H NMe CH CH XXXIX-79 NCOMe H H NMe CH CH XXXIX-80 CH₂ Me H NMe CH CH XXXIX-81 O Me H NMe CH CH XXXIX-82 CHMe Me H NMe CH CH XXXIX-83 CH₂ ═O NMe CH CH XXXIX-84 CH₂ ═CH₂ NMe CH CH XXXIX-85 CH₂ ═CHMe NMe CH CH XXXIX-86 CH₂ H H NMe CF CH XXXIX-87 CHMe H H NMe CF CH XXXIX-88 CHEt H H NMe CF CH XXXIX-89 CHF H H NMe CF CH XXXIX-90 C═CH₂ H H NMe CF CH XXXIX-91 O H H NMe CF CH XXXIX-92 S H H NMe CF CH XXXIX-93 NH H H NMe CF CH XXXIX-94 NMe H H NMe CF CH XXXIX-95 NCHO H H NMe CF CH XXXIX-96 NCOMe H H NMe CF CH XXXIX-97 CH₂ Me H NMe CF CH XXXIX-98 O Me H NMe CF CH XXXIX-99 CHMe Me H NMe CF CH XXXIX-100 CH₂ ═O NMe CF CH XXXIX-101 CH₂ ═CH₂ NMe CF CH XXXIX-102 CH₂ ═CHMe NMe CF CH XXXIX-103 CH₂ H H NMe CMe CH XXXIX-104 CHMe H H NMe CMe CH XXXIX-105 CHEt H H NMe CMe CH XXXIX-106 CHF H H NMe CMe CH XXXIX-107 C═CH₂ H H NMe CMe CH XXXIX-108 O H H NMe CMe CH XXXIX-109 S H H NMe CMe CH XXXIX-110 NH H H NMe CMe CH XXXIX-111 NMe H H NMe CMe CH XXXIX-112 NCHO H H NMe CMe CH XXXIX-113 NCOMe H H NMe CMe CH XXXIX-114 CH₂ Me H NMe CMe CH XXXIX-115 O Me H NMe CMe CH XXXIX-116 CHMe Me H NMe CMe CH XXXIX-117 CH₂ ═O NMe CMe CH XXXIX-118 CH₂ ═CH₂ NMe CMe CH XXXIX-119 CH₂ ═CHMe NMe CMe CH XXXIX-120 CH₂ H H NMe CH CMe XXXIX-121 CHMe H H NMe CH CMe XXXIX-122 CHEt H H NMe CH CMe XXXIX-123 CHF H H NMe CH CMe XXXIX-124 C═CH₂ H H NMe CH CMe XXXIX-125 O H H NMe CH CMe XXXIX-126 S H H NMe CH CMe XXXIX-127 NH H H NMe CH CMe XXXIX-128 NMe H H NMe CH CMe XXXIX-129 NCHO H H NMe CH CMe XXXIX-130 NCOMe H H NMe CH CMe XXXIX-131 CH₂ Me H NMe CH CMe XXXIX-132 O Me H NMe CH CMe XXXIX-133 CHMe Me H NMe CH CMe XXXIX-134 CH₂ ═O NMe CH CMe XXXIX-135 CH₂ ═CH₂ NMe CH CMe XXXIX-136 CH₂ ═CHMe NMe CH CMe XXXIX-137 CH₂ H H O CH CH XXXIX-138 CHMe H H O CH CH XXXIX-139 CHEt H H O CH CH XXXIX-140 CHF H H O CH CH XXXIX-141 C═CH₂ H H O CH CH XXXIX-142 O H H O CH CH XXXIX-143 S H H O CH CH XXXIX-144 NH H H O CH CH XXXIX-145 NMe H H O CH CH XXXIX-146 NCHO H H O CH CH XXXIX-147 NCOMe H H O CH CH XXXIX-148 CH₂ Me H O CH CH XXXIX-149 O Me H O CH CH XXXIX-150 CHMe Me H O CH CH XXXIX-151 CH₂ ═O O CH CH XXXIX-152 CH₂ ═CH₂ O CH CH XXXIX-153 CH₂ ═CHMe O CH CH XXXIX-154 CH₂ H H O CF CH XXXIX-155 CHMe H H O CF CH XXXIX-156 CHEt H H O CF CH XXXIX-157 CHF H H O CF CH XXXIX-158 C═CH₂ H H O CF CH XXXIX-159 O H H O CF CH XXXIX-160 S H H O CF CH XXXIX-161 NH H H O CF CH XXXIX-162 NMe H H O CF CH XXXIX-163 NCHO H H O CF CH XXXIX-164 NCOMe H H O CF CH XXXIX-165 CH₂ Me H O CF CH XXXIX-166 O Me H O CF CH XXXIX-167 CHMe Me H O CF CH XXXIX-168 CH₂ ═O O CF CH XXXIX-169 CH₂ ═CH₂ O CF CH XXXIX-170 CH₂ ═CHMe O CF CH XXXIX-171 CH₂ H H O CMe CH XXXIX-172 CHMe H H O CMe CH XXXIX-173 CHEt H H O CMe CH XXXIX-174 CHF H H O CMe CH XXXIX-175 C═CH₂ H H O CMe CH XXXIX-176 O H H O CMe CH XXXIX-177 S H H O CMe CH XXXIX-178 NH H H O CMe CH XXXIX-179 NMe H H O CMe CH XXXIX-180 NCHO H H O CMe CH XXXIX-181 NCOMe H H O CMe CH XXXIX-182 CH₂ Me H O CMe CH XXXIX-183 O Me H O CMe CH XXXIX-184 CHMe Me H O CMe CH XXXIX-185 CH₂ ═O O CMe CH XXXIX-186 CH₂ ═CH₂ O CMe CH XXXIX-187 CH₂ ═CHMe O CMe CH XXXIX-188 CH₂ H H O CH CMe XXXIX-189 CHMe H H O CH CMe XXXIX-190 CHEt H H O CH CMe XXXIX-191 CHF H H O CH CMe XXXIX-192 C═CH₂ H H O CH CMe XXXIX-193 O H H O CH CMe XXXIX-194 S H H O CH CMe XXXIX-195 NH H H O CH CMe XXXIX-196 NMe H H O CH CMe XXXIX-197 NCHO H H O CH CMe XXXIX-198 NCOMe H H O CH CMe XXXIX-199 CH₂ Me H O CH CMe XXXIX-200 O Me H O CH CMe XXXIX-201 CHMe Me H O CH CMe XXXIX-202 CH₂ ═O O CH CMe XXXIX-203 CH₂ ═CH₂ O CH CMe XXXIX-204 CH₂ ═CHMe O CH CMe XXXIX-205 CH₂ H H S CH CH XXXIX-206 CHMe H H S CH CH XXXIX-207 CHEt H H S CH CH XXXIX-208 CHF H H S CH CH XXXIX-209 C═CH₂ H H S CH CH XXXIX-210 O H H S CH CH XXXIX-211 S H H S CH CH XXXIX-212 NH H H S CH CH XXXIX-213 NMe H H S CH CH XXXIX-214 NCHO H H S CH CH XXXIX-215 NCOMe H H S CH CH XXXIX-216 CH₂ Me H S CH CH XXXIX-217 O Me H S CH CH XXXIX-218 CHMe Me H S CH CH XXXIX-219 CH₂ ═O S CH CH XXXIX-220 CH₂ ═CH₂ S CH CH XXXIX-221 CH₂ ═CHMe S CH CH XXXIX-222 CH₂ H H S CF CH XXXIX-223 CHMe H H S CF CH XXXIX-224 CHEt H H S CF CH XXXIX-225 CHF H H S CF CH XXXIX-226 C═CH₂ H H S CF CH XXXIX-227 O H H S CF CH XXXIX-228 S H H S CF CH XXXIX-229 NH H H S CF CH XXXIX-230 NMe H H S CF CH XXXIX-231 NCHO H H S CF CH XXXIX-232 NCOMe H H S CF CH XXXIX-233 CH₂ Me H S CF CH XXXIX-234 O Me H S CF CH XXXIX-235 CHMe Me H S CF CH XXXIX-236 CH₂ ═O S CF CH XXXIX-237 CH₂ ═CH₂ S CF CH XXXIX-238 CH₂ ═CHMe S CF CH XXXIX-239 CH₂ H H S CMe CH XXXIX-240 CHMe H H S CMe CH XXXIX-241 CHEt H H S CMe CH XXXIX-242 CHF H H S CMe CH XXXIX-243 C═CH₂ H H S CMe CH XXXIX-244 O H H S CMe CH XXXIX-245 S H H S CMe CH XXXIX-246 NH H H S CMe CH XXXIX-247 NMe H H S CMe CH XXXIX-248 NCHO H H S CMe CH XXXIX-249 NCOMe H H S CMe CH XXXIX-250 CH₂ Me H S CMe CH XXXIX-251 O Me H S CMe CH XXXIX-252 CHMe Me H S CMe CH XXXIX-253 CH₂ ═O S CMe CH XXXIX-254 CH₂ ═CH₂ S CMe CH XXXIX-255 CH₂ ═CHMe S CMe CH XXXIX-256 CH₂ H H S CH CMe XXXIX-257 CHMe H H S CH CMe XXXIX-258 CHEt H H S CH CMe XXXIX-259 CHF H H S CH CMe XXXIX-260 C═CH₂ H H S CH CMe XXXIX-261 O H H S CH CMe XXXIX-262 S H H S CH CMe XXXIX-263 NH H H S CH CMe XXXIX-264 NMe H H S CH CMe XXXIX-265 NCHO H H S CH CMe XXXIX-266 NCOMe H H S CH CMe XXXIX-267 CH₂ Me H S CH CMe XXXIX-268 O Me H S CH CMe XXXIX-269 CHMe Me H S CH CMe XXXIX-270 CH₂ ═O S CH CMe XXXIX-271 CH₂ ═CH₂ S CH CMe XXXIX-272 CH₂ ═CHMe S CH CMe XXXIX-273 CH₂ H H NH N CH XXXIX-274 CHMe H H NH N CH XXXIX-275 CHEt H H NH N CH XXXIX-276 CHF H H NH N CH XXXIX-277 C═CH₂ H H NH N CH XXXIX-278 O H H NH N CH XXXIX-279 S H H NH N CH XXXIX-280 NH H H NH N CH XXXIX-281 NMe H H NH N CH XXXIX-282 NCHO H H NH N CH XXXIX-283 NCOMe H H NH N CH XXXIX-284 CH₂ Me H NH N CH XXXIX-285 O Me H NH N CH XXXIX-286 CHMe Me H NH N CH XXXIX-287 CH₂ ═O NH N CH XXXIX-288 CH₂ ═CH₂ NH N CH XXXIX-289 CH₂ ═CHMe NH N CH XXXIX-290 CH₂ H H NH N CMe XXXIX-291 CHMe H H NH N CMe XXXIX-292 CHEt H H NH N CMe XXXIX-293 CHF H H NH N CMe XXXIX-294 C═CH₂ H H NH N CMe XXXIX-295 O H H NH N CMe XXXIX-296 S H H NH N CMe XXXIX-297 NH H H NH N CMe XXXIX-298 NMe H H NH N CMe XXXIX-299 NCHO H H NH N CMe XXXIX-300 NCOMe H H NH N CMe XXXIX-301 CH₂ Me H NH N CMe XXXIX-302 O Me H NH N CMe XXXIX-303 CHMe Me H NH N CMe XXXIX-304 CH₂ ═O NH N CMe XXXIX-305 CH₂ ═CH₂ NH N CMe XXXIX-306 CH₂ ═CHMe NH N CMe XXXIX-307 CH₂ H H NMe N CH XXXIX-308 CHMe H H NMe N CH XXXIX-309 CHEt H H NMe N CH XXXIX-310 CHF H H NMe N CH XXXIX-311 C═CH₂ H H NMe N CH XXXIX-312 O H H NMe N CH XXXIX-313 S H H NMe N CH XXXIX-314 NH H H NMe N CH XXXIX-315 NMe H H NMe N CH XXXIX-316 NCHO H H NMe N CH XXXIX-317 NCOMe H H NMe N CH XXXIX-318 CH₂ Me H NMe N CH XXXIX-319 O Me H NMe N CH XXXIX-320 CHMe Me H NMe N CH XXXIX-321 CH₂ ═O NMe N CH XXXIX-322 CH₂ ═CH₂ NMe N CH XXXIX-323 CH₂ ═CHMe NMe N CH XXXIX-324 CH₂ H H NMe N CMe XXXIX-325 CHMe H H NMe N CMe XXXIX-326 CHEt H H NMe N CMe XXXIX-327 CHF H H NMe N CMe XXXIX-328 C═CH₂ H H NMe N CMe XXXIX-329 O H H NMe N CMe XXXIX-330 S H H NMe N CMe XXXIX-331 NH H H NMe N CMe XXXIX-332 NMe H H NMe N CMe XXXIX-333 NCHO H H NMe N CMe XXXIX-334 NCOMe H H NMe N CMe XXXIX-335 CH₂ Me H NMe N CMe XXXIX-336 O Me H NMe N CMe XXXIX-337 CHMe Me H NMe N CMe XXXIX-338 CH₂ ═O NMe N CMe XXXIX-339 CH₂ ═CH₂ NMe N CMe XXXIX-340 CH₂ ═CHMe NMe N CMe XXXIX-341 CH₂ H H O N CH XXXIX-342 CHMe H H O N CH XXXIX-343 CHEt H H O N CH XXXIX-344 CHF H H O N CH XXXIX-345 C═CH₂ H H O N CH XXXIX-346 O H H O N CH XXXIX-347 S H H O N CH XXXIX-348 NH H H O N CH XXXIX-349 NMe H H O N CH XXXIX-350 NCHO H H O N CH XXXIX-351 NCOMe H H O N CH XXXIX-352 CH₂ Me H O N CH XXXIX-353 O Me H O N CH XXXIX-354 CHMe Me H O N CH XXXIX-355 CH₂ ═O O N CH XXXIX-356 CH₂ ═CH₂ O N CH XXXIX-357 CH₂ ═CHMe O N CH XXXIX-358 CH₂ H H O N CMe XXXIX-359 CHMe H H O N CMe XXXIX-360 CHEt H H O N CMe XXXIX-361 CHF H H O N CMe XXXIX-362 C═CH₂ H H O N CMe XXXIX-363 O H H O N CMe XXXIX-364 S H H O N CMe XXXIX-365 NH H H O N CMe XXXIX-366 NMe H H O N CMe XXXIX-367 NCHO H H O N CMe XXXIX-368 NCOMe H H O N CMe XXXIX-369 CH₂ Me H O N CMe XXXIX-370 O Me H O N CMe XXXIX-371 CHMe Me H O N CMe XXXIX-372 CH₂ ═O O N CMe XXXIX-373 CH₂ ═CH₂ O N CMe XXXIX-374 CH₂ ═CHMe O N CMe XXXIX-375 CH₂ H H S N CH XXXIX-376 CHMe H H S N CH XXXIX-377 CHEt H H S N CH XXXIX-378 CHF H H S N CH XXXIX-379 C═CH₂ H H S N CH XXXIX-380 O H H S N CH XXXIX-381 S H H S N CH XXXIX-382 NH H H S N CH XXXIX-383 NMe H H S N CH XXXIX-384 NCHO H H S N CH XXXIX-385 NCOMe H H S N CH XXXIX-386 CH₂ Me H S N CH XXXIX-387 O Me H S N CH XXXIX-388 CHMe Me H S N CH XXXIX-389 CH₂ ═O S N CH XXXIX-390 CH₂ ═CH₂ S N CH XXXIX-391 CH₂ ═CHMe S N CH XXXIX-392 CH₂ H H S N CMe XXXIX-393 CHMe H H S N CMe XXXIX-394 CHEt H H S N CMe XXXIX-395 CHF H H S N CMe XXXIX-396 C═CH₂ H H S N CMe XXXIX-397 O H H S N CMe XXXIX-398 S H H S N CMe XXXIX-399 NH H H S N CMe XXXIX-400 NMe H H S N CMe XXXIX-401 NCHO H H S N CMe XXXIX-402 NCOMe H H S N CMe XXXIX-403 CH₂ Me H S N CMe XXXIX-404 O Me H S N CMe XXXIX-405 CHMe Me H S N CMe XXXIX-406 CH₂ ═O S N CMe XXXIX-407 CH₂ ═CH₂ S N CMe XXXIX-408 CH₂ ═CHMe S N CMe XXXIX-409 CH₂ H H NH CH N XXXIX-410 CHMe H H NH CH N XXXIX-411 CHEt H H NH CH N XXXIX-412 CHF H H NH CH N XXXIX-413 C═CH₂ H H NH CH N XXXIX-414 O H H NH CH N XXXIX-415 S H H NH CH N XXXIX-416 NH H H NH CH N XXXIX-417 NMe H H NH CH N XXXIX-418 NCHO H H NH CH N XXXIX-419 NCOMe H H NH CH N XXXIX-420 CH₂ Me H NH CH N XXXIX-421 O Me H NH CH N XXXIX-422 CHMe Me H NH CH N XXXIX-423 CH₂ ═O NH CH N XXXIX-424 CH₂ ═CH₂ NH CH N XXXIX-425 CH₂ ═CHMe NH CH N XXXIX-426 CH₂ H H NH CMe N XXXIX-427 CHMe H H NH CMe N XXXIX-428 CHEt H H NH CMe N XXXIX-429 CHF H H NH CMe N XXXIX-430 C═CH₂ H H NH CMe N XXXIX-431 O H H NH CMe N XXXIX-432 S H H NH CMe N XXXIX-433 NH H H NH CMe N XXXIX-434 NMe H H NH CMe N XXXIX-435 NCHO H H NH CMe N XXXIX-436 NCOMe H H NH CMe N XXXIX-437 CH₂ Me H NH CMe N XXXIX-438 O Me H NH CMe N XXXIX-439 CHMe Me H NH CMe N XXXIX-440 CH₂ ═O NH CMe N XXXIX-441 CH₂ ═CH₂ NH CMe N XXXIX-442 CH₂ ═CHMe NH CMe N XXXIX-443 CH₂ H H O CH N XXXIX-444 CHMe H H O CH N XXXIX-445 CHEt H H O CH N XXXIX-446 CHF H H O CH N XXXIX-447 C═CH₂ H H O CH N XXXIX-448 O H H O CH N XXXIX-449 S H H O CH N XXXIX-450 NH H H O CH N XXXIX-451 NMe H H O CH N XXXIX-452 NCHO H H O CH N XXXIX-453 NCOMe H H O CH N XXXIX-454 CH₂ Me H O CH N XXXIX-455 O Me H O CH N XXXIX-456 CHMe Me H O CH N XXXIX-457 CH₂ ═O O CH N XXXIX-458 CH₂ ═CH₂ O CH N XXXIX-459 CH₂ ═CHMe O CH N XXXIX-460 CH₂ H H O CMe N XXXIX-461 CHMe H H O CMe N XXXIX-462 CHEt H H O CMe N XXXIX-463 CHF H H O CMe N XXXIX-464 C═CH₂ H H O CMe N XXXIX-465 O H H O CMe N XXXIX-466 S H H O CMe N XXXIX-467 NH H H O CMe N XXXIX-468 NMe H H O CMe N XXXIX-469 NCHO H H O CMe N XXXIX-470 NCOMe H H O CMe N XXXIX-471 CH₂ Me H O CMe N XXXIX-472 O Me H O CMe N XXXIX-473 CHMe Me H O CMe N XXXIX-474 CH₂ ═O O CMe N XXXIX-475 CH₂ ═CH₂ O CMe N XXXIX-476 CH₂ ═CHMe O CMe N XXXIX-477 CH₂ H H S CH N XXXIX-478 CHMe H H S CH N XXXIX-479 CHEt H H S CH N XXXIX-480 CHF H H S CH N XXXIX-481 C═CH₂ H H S CH N XXXIX-482 O H H S CH N XXXIX-483 S H H S CH N XXXIX-484 NH H H S CH N XXXIX-485 NMe H H S CH N XXXIX-486 NCHO H H S CH N XXXIX-487 NCOMe H H S CH N XXXIX-488 CH₂ Me H S CH N XXXIX-489 O Me H S CH N XXXIX-490 CHMe Me H S CH N XXXIX-491 CH₂ ═O S CH N XXXIX-492 CH₂ ═CH₂ S CH N XXXIX-493 CH₂ ═CHMe S CH N XXXIX-494 CH₂ H H S CMe N XXXIX-495 CHMe H H S CMe N XXXIX-496 CHEt H H S CMe N XXXIX-497 CHF H H S CMe N XXXIX-498 C═CH₂ H H S CMe N XXXIX-499 O H H S CMe N XXXIX-500 S H H S CMe N XXXIX-501 NH H H S CMe N XXXIX-502 NMe H H S CMe N XXXIX-503 NCHO H H S CMe N XXXIX-504 NCOMe H H S CMe N XXXIX-505 CH₂ Me H S CMe N XXXIX-506 O Me H S CMe N XXXIX-507 CHMe Me H S CMe N XXXIX-508 CH₂ ═O S CMe N XXXIX-509 CH₂ ═CH₂ S CMe N XXXIX-510 CH₂ ═CHMe S CMe N XXXIX-511 CH₂ H H NH N N XXXIX-512 CHMe H H NH N N XXXIX-513 CHEt H H NH N N XXXIX-514 CHF H H NH N N XXXIX-515 C═CH₂ H H NH N N XXXIX-516 O H H NH N N XXXIX-517 S H H NH N N XXXIX-518 NH H H NH N N XXXIX-519 NMe H H NH N N XXXIX-520 NCHO H H NH N N XXXIX-521 NCOMe H H NH N N XXXIX-522 CH₂ Me H NH N N XXXIX-523 O Me H NH N N XXXIX-524 CHMe Me H NH N N XXXIX-525 CH₂ ═O NH N N XXXIX-526 CH₂ ═CH₂ NH N N XXXIX-527 CH₂ ═CHMe NH N N XXXIX-528 CH₂ H H NMe N N XXXIX-529 CHMe H H NMe N N XXXIX-530 CHEt H H NMe N N XXXIX-531 CHF H H NMe N N XXXIX-532 C═CH₂ H H NMe N N XXXIX-533 O H H NMe N N XXXIX-534 S H H NMe N N XXXIX-535 NH H H NMe N N XXXIX-536 NMe H H NMe N N XXXIX-537 NCHO H H NMe N N XXXIX-538 NCOMe H H NMe N N XXXIX-539 CH₂ Me H NMe N N XXXIX-540 O Me H NMe N N XXXIX-541 CHMe Me H NMe N N XXXIX-542 CH₂ ═O NMe N N XXXIX-543 CH₂ ═CH₂ NMe N N XXXIX-544 CH₂ ═CHMe NMe N N XXXIX-545 CH₂ H H O N N XXXIX-546 CHMe H H O N N XXXIX-547 CHEt H H O N N XXXIX-548 CHF H H O N N XXXIX-549 C═CH₂ H H O N N XXXIX-550 O H H O N N XXXIX-551 S H H O N N XXXIX-552 NH H H O N N XXXIX-553 NMe H H O N N XXXIX-554 NCHO H H O N N XXXIX-555 NCOMe H H O N N XXXIX-556 CH₂ Me H O N N XXXIX-557 O Me H O N N XXXIX-558 CHMe Me H O N N XXXIX-559 CH₂ ═O O N N XXXIX-560 CH₂ ═CH₂ O N N XXXIX-561 CH₂ ═CHMe O N N XXXIX-562 CH₂ H H S N N XXXIX-563 CHMe H H S N N XXXIX-564 CHEt H H S N N XXXIX-565 CHF H H S N N XXXIX-566 C═CH₂ H H S N N XXXIX-567 O H H S N N XXXIX-568 S H H S N N XXXIX-569 NH H H S N N XXXIX-570 NMe H H S N N XXXIX-571 NCHO H H S N N XXXIX-572 NCOMe H H S N N XXXIX-573 CH₂ Me H S N N XXXIX-574 O Me H S N N XXXIX-575 CHMe Me H S N N XXXIX-576 CH₂ ═O S N N XXXIX-577 CH₂ ═CH₂ S N N XXXIX-578 CH₂ ═CHMe S N N

Table XL provides 392 compounds of formula Ian

wherein the values of Y, R¹, R₂, T^(d), T^(e) and T^(f) are given in Table 7.

TABLE 7 Compound No Y R1 R2 Td Te Tf XL-1 CH₂ H H CH NH CH XL-2 CHMe H H CH NH CH XL-3 CHEt H H CH NH CH XL-4 CHF H H CH NH CH XL-5 C═CH₂ H H CH NH CH XL-6 O H H CH NH CH XL-7 S H H CH NH CH XL-8 NH H H CH NH CH XL-9 NMe H H CH NH CH XL-10 NCHO H H CH NH CH XL-11 NCOMe H H CH NH CH XL-12 CH₂ Me H CH NH CH XL-13 O Me H CH NH CH XL-14 CHMe Me H CH NH CH XL-15 CH₂ H H CMe NH CH XL-16 CHMe H H CMe NH CH XL-17 CHEt H H CMe NH CH XL-18 CHF H H CMe NH CH XL-19 C═CH₂ H H CMe NH CH XL-20 O H H CMe NH CH XL-21 S H H CMe NH CH XL-22 NH H H CMe NH CH XL-23 NMe H H CMe NH CH XL-24 NCHO H H CMe NH CH XL-25 NCOMe H H CMe NH CH XL-26 CH₂ Me H CMe NH CH XL-27 O Me H CMe NH CH XL-28 CHMe Me H CMe NH CH XL-29 CH₂ H H CH NH CMe XL-30 CHMe H H CH NH CMe XL-31 CHEt H H CH NH CMe XL-32 CHF H H CH NH CMe XL-33 C═CH₂ H H CH NH CMe XL-34 O H H CH NH CMe XL-35 S H H CH NH CMe XL-36 NH H H CH NH CMe XL-37 NMe H H CH NH CMe XL-38 NCHO H H CH NH CMe XL-39 NCOMe H H CH NH CMe XL-40 CH₂ Me H CH NH CMe XL-41 O Me H CH NH CMe XL-42 CHMe Me H CH NH CMe XL-43 CH₂ H H CMe NH CMe XL-44 CHMe H H CMe NH CMe XL-45 CHEt H H CMe NH CMe XL-46 CHF H H CMe NH CMe XL-47 C═CH₂ H H CMe NH CMe XL-48 O H H CMe NH CMe XL-49 S H H CMe NH CMe XL-50 NH H H CMe NH CMe XL-51 NMe H H CMe NH CMe XL-52 NCHO H H CMe NH CMe XL-53 NCOMe H H CMe NH CMe XL-54 CH₂ Me H CMe NH CMe XL-55 O Me H CMe NH CMe XL-56 CHMe Me H CMe NH CMe XL-57 CH₂ H H CH NMe CH XL-58 CHMe H H CH NMe CH XL-59 CHEt H H CH NMe CH XL-60 CHF H H CH NMe CH XL-61 C═CH₂ H H CH NMe CH XL-62 O H H CH NMe CH XL-63 S H H CH NMe CH XL-64 NH H H CH NMe CH XL-65 NMe H H CH NMe CH XL-66 NCHO H H CH NMe CH XL-67 NCOMe H H CH NMe CH XL-68 CH₂ Me H CH NMe CH XL-69 O Me H CH NMe CH XL-70 CHMe Me H CH NMe CH XL-71 CH₂ H H CMe NMe CH XL-72 CHMe H H CMe NMe CH XL-73 CHEt H H CMe NMe CH XL-74 CHF H H CMe NMe CH XL-75 C═CH₂ H H CMe NMe CH XL-76 O H H CMe NMe CH XL-77 S H H CMe NMe CH XL-78 NH H H CMe NMe CH XL-79 NMe H H CMe NMe CH XL-80 NCHO H H CMe NMe CH XL-81 NCOMe H H CMe NMe CH XL-82 CH₂ Me H CMe NMe CH XL-83 O Me H CMe NMe CH XL-84 CHMe Me H CMe NMe CH XL-85 CH₂ H H CH NMe CMe XL-86 CHMe H H CH NMe CMe XL-87 CHEt H H CH NMe CMe XL-88 CHF H H CH NMe CMe XL-89 C═CH₂ H H CH NMe CMe XL-90 O H H CH NMe CMe XL-91 S H H CH NMe CMe XL-92 NH H H CH NMe CMe XL-93 NMe H H CH NMe CMe XL-94 NCHO H H CH NMe CMe XL-95 NCOMe H H CH NMe CMe XL-96 CH₂ Me H CH NMe CMe XL-97 O Me H CH NMe CMe XL-98 CHMe Me H CH NMe CMe XL-99 CH₂ H H CMe NMe CMe XL-100 CHMe H H CMe NMe CMe XL-101 CHEt H H CMe NMe CMe XL-102 CHF H H CMe NMe CMe XL-103 C═CH₂ H H CMe NMe CMe XL-104 O H H CMe NMe CMe XL-105 S H H CMe NMe CMe XL-106 NH H H CMe NMe CMe XL-107 NMe H H CMe NMe CMe XL-108 NCHO H H CMe NMe CMe XL-109 NCOMe H H CMe NMe CMe XL-110 CH₂ Me H CMe NMe CMe XL-111 O Me H CMe NMe CMe XL-112 CHMe Me H CMe NMe CMe XL-113 CH₂ H H CH O CH XL-114 CHMe H H CH O CH XL-115 CHEt H H CH O CH XL-116 CHF H H CH O CH XL-117 C═CH₂ H H CH O CH XL-118 O H H CH O CH XL-119 S H H CH O CH XL-120 NH H H CH O CH XL-121 NMe H H CH O CH XL-122 NCHO H H CH O CH XL-123 NCOMe H H CH O CH XL-124 CH₂ Me H CH O CH XL-125 O Me H CH O CH XL-126 CHMe Me H CH O CH XL-127 CH₂ H H CMe O CH XL-128 CHMe H H CMe O CH XL-129 CHEt H H CMe O CH XL-130 CHF H H CMe O CH XL-131 C═CH₂ H H CMe O CH XL-132 O H H CMe O CH XL-133 S H H CMe O CH XL-134 NH H H CMe O CH XL-135 NMe H H CMe O CH XL-136 NCHO H H CMe O CH XL-137 NCOMe H H CMe O CH XL-138 CH₂ Me H CMe O CH XL-139 O Me H CMe O CH XL-140 CHMe Me H CMe O CH XL-141 CH₂ H H CH O CMe XL-142 CHMe H H CH O CMe XL-143 CHEt H H CH O CMe XL-144 CHF H H CH O CMe XL-145 C═CH₂ H H CH O CMe XL-146 O H H CH O CMe XL-147 S H H CH O CMe XL-148 NH H H CH O CMe XL-149 NMe H H CH O CMe XL-150 NCHO H H CH O CMe XL-151 NCOMe H H CH O CMe XL-152 CH₂ Me H CH O CMe XL-153 O Me H CH O CMe XL-154 CHMe Me H CH O CMe XL-155 CH₂ H H CMe O CMe XL-156 CHMe H H CMe O CMe XL-157 CHEt H H CMe O CMe XL-158 CHF H H CMe O CMe XL-159 C═CH₂ H H CMe O CMe XL-160 O H H CMe O CMe XL-161 S H H CMe O CMe XL-162 NH H H CMe O CMe XL-163 NMe H H CMe O CMe XL-164 NCHO H H CMe O CMe XL-165 NCOMe H H CMe O CMe XL-166 CH₂ Me H CMe O CMe XL-167 O Me H CMe O CMe XL-168 CHMe Me H CMe O CMe XL-169 CH₂ H H CH S CH XL-170 CHMe H H CH S CH XL-171 CHEt H H CH S CH XL-172 CHF H H CH S CH XL-173 C═CH₂ H H CH S CH XL-174 O H H CH S CH XL-175 S H H CH S CH XL-176 NH H H CH S CH XL-177 NMe H H CH S CH XL-178 NCHO H H CH S CH XL-179 NCOMe H H CH S CH XL-180 CH₂ Me H CH S CH XL-181 O Me H CH S CH XL-182 CHMe Me H CH S CH XL-183 CH₂ H H CMe S CH XL-184 CHMe H H CMe S CH XL-185 CHEt H H CMe S CH XL-186 CHF H H CMe S CH XL-187 C═CH₂ H H CMe S CH XL-188 O H H CMe S CH XL-189 S H H CMe S CH XL-190 NH H H CMe S CH XL-191 NMe H H CMe S CH XL-192 NCHO H H CMe S CH XL-193 NCOMe H H CMe S CH XL-194 CH₂ Me H CMe S CH XL-195 O Me H CMe S CH XL-196 CHMe Me H CMe S CH XL-197 CH₂ H H CH S CMe XL-198 CHMe H H CH S CMe XL-199 CHEt H H CH S CMe XL-200 CHF H H CH S CMe XL-201 C═CH₂ H H CH S CMe XL-202 O H H CH S CMe XL-203 S H H CH S CMe XL-204 NH H H CH S CMe XL-205 NMe H H CH S CMe XL-206 NCHO H H CH S CMe XL-207 NCOMe H H CH S CMe XL-208 CH₂ Me H CH S CMe XL-209 O Me H CH S CMe XL-210 CHMe Me H CH S CMe XL-211 CH₂ H H CMe S CMe XL-212 CHMe H H CMe S CMe XL-213 CHEt H H CMe S CMe XL-214 CHF H H CMe S CMe XL-215 C═CH₂ H H CMe S CMe XL-216 O H H CMe S CMe XL-217 S H H CMe S CMe XL-218 NH H H CMe S CMe XL-219 NMe H H CMe S CMe XL-220 NCHO H H CMe S CMe XL-221 NCOMe H H CMe S CMe XL-222 CH₂ Me H CMe S CMe XL-223 O Me H CMe S CMe XL-224 CHMe Me H CMe S CMe XL-225 CH₂ H H N NMe CH XL-226 CHMe H H N NMe CH XL-227 CHEt H H N NMe CH XL-228 CHF H H N NMe CH XL-229 C═CH₂ H H N NMe CH XL-230 O H H N NMe CH XL-231 S H H N NMe CH XL-232 NH H H N NMe CH XL-233 NMe H H N NMe CH XL-234 NCHO H H N NMe CH XL-235 NCOMe H H N NMe CH XL-236 CH₂ Me H N NMe CH XL-237 O Me H N NMe CH XL-238 CHMe Me H N NMe CH XL-239 CH₂ H H N NMe CMe XL-240 CHMe H H N NMe CMe XL-241 CHEt H H N NMe CMe XL-242 CHF H H N NMe CMe XL-243 C═CH₂ H H N NMe CMe XL-244 O H H N NMe CMe XL-245 S H H N NMe CMe XL-246 NH H H N NMe CMe XL-247 NMe H H N NMe CMe XL-248 NCHO H H N NMe CMe XL-249 NCOMe H H N NMe CMe XL-250 CH₂ Me H N NMe CMe XL-251 O Me H N NMe CMe XL-252 CHMe Me H N NMe CMe XL-253 CH₂ H H N O CH XL-254 CHMe H H N O CH XL-255 CHEt H H N O CH XL-256 CHF H H N O CH XL-257 C═CH₂ H H N O CH XL-258 O H H N O CH XL-259 S H H N O CH XL-260 NH H H N O CH XL-261 NMe H H N O CH XL-262 NCHO H H N O CH XL-263 NCOMe H H N O CH XL-264 CH₂ Me H N O CH XL-265 O Me H N O CH XL-266 CHMe Me H N O CH XL-267 CH₂ H H N O CMe XL-268 CHMe H H N O CMe XL-269 CHEt H H N O CMe XL-270 CHF H H N O CMe XL-271 C═CH₂ H H N O CMe XL-272 O H H N O CMe XL-273 S H H N O CMe XL-274 NH H H N O CMe XL-275 NMe H H N O CMe XL-276 NCHO H H N O CMe XL-277 NCOMe H H N O CMe XL-278 CH₂ Me H N O CMe XL-279 O Me H N O CMe XL-280 CHMe Me H N O CMe XL-281 CH₂ H H N S CH XL-282 CHMe H H N S CH XL-283 CHEt H H N S CH XL-284 CHF H H N S CH XL-285 C═CH₂ H H N S CH XL-286 O H H N S CH XL-287 S H H N S CH XL-288 NH H H N S CH XL-289 NMe H H N S CH XL-290 NCHO H H N S CH XL-291 NCOMe H H N S CH XL-292 CH₂ Me H N S CH XL-293 O Me H N S CH XL-294 CHMe Me H N S CH XL-295 CH₂ H H N S CMe XL-296 CHMe H H N S CMe XL-297 CHEt H H N S CMe XL-298 CHF H H N S CMe XL-299 C═CH₂ H H N S CMe XL-300 O H H N S CMe XL-301 S H H N S CMe XL-302 NH H H N S CMe XL-303 NMe H H N S CMe XL-304 NCHO H H N S CMe XL-305 NCOMe H H N S CMe XL-306 CH₂ Me H N S CMe XL-307 O Me H N S CMe XL-308 CHMe Me H N S CMe XL-309 CH₂ H H CH NMe N XL-310 CHMe H H CH NMe N XL-311 CHEt H H CH NMe N XL-312 CHF H H CH NMe N XL-313 C═CH₂ H H CH NMe N XL-314 O H H CH NMe N XL-315 S H H CH NMe N XL-316 NH H H CH NMe N XL-317 NMe H H CH NMe N XL-318 NCHO H H CH NMe N XL-319 NCOMe H H CH NMe N XL-320 CH₂ Me H CH NMe N XL-321 O Me H CH NMe N XL-322 CHMe Me H CH NMe N XL-323 CH₂ H H CMe NMe N XL-324 CHMe H H CMe NMe N XL-325 CHEt H H CMe NMe N XL-326 CHF H H CMe NMe N XL-327 C═CH₂ H H CMe NMe N XL-328 O H H CMe NMe N XL-329 S H H CMe NMe N XL-330 NH H H CMe NMe N XL-331 NMe H H CMe NMe N XL-332 NCHO H H CMe NMe N XL-333 NCOMe H H CMe NMe N XL-334 CH₂ Me H CMe NMe N XL-335 O Me H CMe NMe N XL-336 CHMe Me H CMe NMe N XL-337 CH₂ H H CH O N XL-338 CHMe H H CH O N XL-339 CHEt H H CH O N XL-340 CHF H H CH O N XL-341 C═CH₂ H H CH O N XL-342 O H H CH O N XL-343 S H H CH O N XL-344 NH H H CH O N XL-345 NMe H H CH O N XL-346 NCHO H H CH O N XL-347 NCOMe H H CH O N XL-348 CH₂ Me H CH O N XL-349 O Me H CH O N XL-350 CHMe Me H CH O N XL-351 CH₂ H H CMe O N XL-352 CHMe H H CMe O N XL-353 CHEt H H CMe O N XL-354 CHF H H CMe O N XL-355 C═CH₂ H H CMe O N XL-356 O H H CMe O N XL-357 S H H CMe O N XL-358 NH H H CMe O N XL-359 NMe H H CMe O N XL-360 NCHO H H CMe O N XL-361 NCOMe H H CMe O N XL-362 CH₂ Me H CMe O N XL-363 O Me H CMe O N XL-364 CHMe Me H CMe O N XL-365 CH₂ H H CH S N XL-366 CHMe H H CH S N XL-367 CHEt H H CH S N XL-368 CHF H H CH S N XL-369 C═CH₂ H H CH S N XL-370 O H H CH S N XL-371 S H H CH S N XL-372 NH H H CH S N XL-373 NMe H H CH S N XL-374 NCHO H H CH S N XL-375 NCOMe H H CH S N XL-376 CH₂ Me H CH S N XL-377 O Me H CH S N XL-378 CHMe Me H CH S N XL-379 CH₂ H H CMe S N XL-380 CHMe H H CMe S N XL-381 CHEt H H CMe S N XL-382 CHF H H CMe S N XL-383 C═CH₂ H H CMe S N XL-384 O H H CMe S N XL-385 S H H CMe S N XL-386 NH H H CMe S N XL-387 NMe H H CMe S N XL-388 NCHO H H CMe S N XL-389 NCOMe H H CMe S N XL-390 CH₂ Me H CMe S N XL-391 O Me H CMe S N XL-392 CHMe Me H CMe S N

Table XLI provides 336 compounds of formula Iao

wherein the values of Y, R¹, R², T^(d), T^(e) and T^(f) are given in Table 8.

TABLE 8 Compound No Y R1 R2 Td Te Tf XLI-1 CH₂ H H CH CH NH XLI-2 CHMe H H CH CH NH XLI-3 CHEt H H CH CH NH XLI-4 CHF H H CH CH NH XLI-5 C═CH₂ H H CH CH NH XLI-6 O H H CH CH NH XLI-7 S H H CH CH NH XLI-8 NH H H CH CH NH XLI-9 NMe H H CH CH NH XLI-10 NCHO H H CH CH NH XLI-11 NCOMe H H CH CH NH XLI-12 CH₂ Me H CH CH NH XLI-13 O Me H CH CH NH XLI-14 CHMe Me H CH CH NH XLI-15 CH₂ H H CMe CH NH XLI-16 CHMe H H CMe CH NH XLI-17 CHEt H H CMe CH NH XLI-18 CHF H H CMe CH NH XLI-19 C═CH₂ H H CMe CH NH XLI-20 O H H CMe CH NH XLI-21 S H H CMe CH NH XLI-22 NH H H CMe CH NH XLI-23 NMe H H CMe CH NH XLI-24 NCHO H H CMe CH NH XLI-25 NCOMe H H CMe CH NH XLI-26 CH₂ Me H CMe CH NH XLI-27 O Me H CMe CH NH XLI-28 CHMe Me H CMe CH NH XLI-29 CH₂ H H CH CMe NH XLI-30 CHMe H H CH CMe NH XLI-31 CHEt H H CH CMe NH XLI-32 CHF H H CH CMe NH XLI-33 C═CH₂ H H CH CMe NH XLI-34 O H H CH CMe NH XLI-35 S H H CH CMe NH XLI-36 NH H H CH CMe NH XLI-37 NMe H H CH CMe NH XLI-38 NCHO H H CH CMe NH XLI-39 NCOMe H H CH CMe NH XLI-40 CH₂ Me H CH CMe NH XLI-41 O Me H CH CMe NH XLI-42 CHMe Me H CH CMe NH XLI-43 CH₂ H H CH CH NMe XLI-44 CHMe H H CH CH NMe XLI-45 CHEt H H CH CH NMe XLI-46 CHF H H CH CH NMe XLI-47 C═CH₂ H H CH CH NMe XLI-48 O H H CH CH NMe XLI-49 S H H CH CH NMe XLI-50 NH H H CH CH NMe XLI-51 NMe H H CH CH NMe XLI-52 NCHO H H CH CH NMe XLI-53 NCOMe H H CH CH NMe XLI-54 CH₂ Me H CH CH NMe XLI-55 O Me H CH CH NMe XLI-56 CHMe Me H CH CH NMe XLI-57 CH₂ H H CMe CH NMe XLI-58 CHMe H H CMe CH NMe XLI-59 CHEt H H CMe CH NMe XLI-60 CHF H H CMe CH NMe XLI-61 C═CH₂ H H CMe CH NMe XLI-62 O H H CMe CH NMe XLI-63 S H H CMe CH NMe XLI-64 NH H H CMe CH NMe XLI-65 NMe H H CMe CH NMe XLI-66 NCHO H H CMe CH NMe XLI-67 NCOMe H H CMe CH NMe XLI-68 CH₂ Me H CMe CH NMe XLI-69 O Me H CMe CH NMe XLI-70 CHMe Me H CMe CH NMe XLI-71 CH₂ H H CH CMe NMe XLI-72 CHMe H H CH CMe NMe XLI-73 CHEt H H CH CMe NMe XLI-74 CHF H H CH CMe NMe XLI-75 C═CH₂ H H CH CMe NMe XLI-76 O H H CH CMe NMe XLI-77 S H H CH CMe NMe XLI-78 NH H H CH CMe NMe XLI-79 NMe H H CH CMe NMe XLI-80 NCHO H H CH CMe NMe XLI-81 NCOMe H H CH CMe NMe XLI-82 CH₂ Me H CH CMe NMe XLI-83 O Me H CH CMe NMe XLI-84 CHMe Me H CH CMe NMe XLI-85 CH₂ H H CH CH O XLI-86 CHMe H H CH CH O XLI-87 CHEt H H CH CH O XLI-88 CHF H H CH CH O XLI-89 C═CH₂ H H CH CH O XLI-90 O H H CH CH O XLI-91 S H H CH CH O XLI-92 NH H H CH CH O XLI-93 NMe H H CH CH O XLI-94 NCHO H H CH CH O XLI-95 NCOMe H H CH CH O XLI-96 CH₂ Me H CH CH O XLI-97 O Me H CH CH O XLI-98 CHMe Me H CH CH O XLI-99 CH₂ H H CMe CH O XLI-100 CHMe H H CMe CH O XLI-101 CHEt H H CMe CH O XLI-102 CHF H H CMe CH O XLI-103 C═CH₂ H H CMe CH O XLI-104 O H H CMe CH O XLI-105 S H H CMe CH O XLI-106 NH H H CMe CH O XLI-107 NMe H H CMe CH O XLI-108 NCHO H H CMe CH O XLI-109 NCOMe H H CMe CH O XLI-110 CH₂ Me H CMe CH O XLI-111 O Me H CMe CH O XLI-112 CHMe Me H CMe CH O XLI-113 CH₂ H H CH CMe O XLI-114 CHMe H H CH CMe O XLI-115 CHEt H H CH CMe O XLI-116 CHF H H CH CMe O XLI-117 C═CH₂ H H CH CMe O XLI-118 O H H CH CMe O XLI-119 S H H CH CMe O XLI-120 NH H H CH CMe O XLI-121 NMe H H CH CMe O XLI-122 NCHO H H CH CMe O XLI-123 NCOMe H H CH CMe O XLI-124 CH₂ Me H CH CMe O XLI-125 O Me H CH CMe O XLI-126 CHMe Me H CH CMe O XLI-127 CH₂ H H CH CH S XLI-128 CHMe H H CH CH S XLI-129 CHEt H H CH CH S XLI-130 CHF H H CH CH S XLI-131 C═CH₂ H H CH CH S XLI-132 O H H CH CH S XLI-133 S H H CH CH S XLI-134 NH H H CH CH S XLI-135 NMe H H CH CH S XLI-136 NCHO H H CH CH S XLI-137 NCOMe H H CH CH S XLI-138 CH₂ Me H CH CH S XLI-139 O Me H CH CH S XLI-140 CHMe Me H CH CH S XLI-141 CH₂ H H CMe CH S XLI-142 CHMe H H CMe CH S XLI-143 CHEt H H CMe CH S XLI-144 CHF H H CMe CH S XLI-145 C═CH₂ H H CMe CH S XLI-146 O H H CMe CH S XLI-147 S H H CMe CH S XLI-148 NH H H CMe CH S XLI-149 NMe H H CMe CH S XLI-150 NCHO H H CMe CH S XLI-151 NCOMe H H CMe CH S XLI-152 CH₂ Me H CMe CH S XLI-153 O Me H CMe CH S XLI-154 CHMe Me H CMe CH S XLI-155 CH₂ H H CH CMe S XLI-156 CHMe H H CH CMe S XLI-157 CHEt H H CH CMe S XLI-158 CHF H H CH CMe S XLI-159 C═CH₂ H H CH CMe S XLI-160 O H H CH CMe S XLI-161 S H H CH CMe S XLI-162 NH H H CH CMe S XLI-163 NMe H H CH CMe S XLI-164 NCHO H H CH CMe S XLI-165 NCOMe H H CH CMe S XLI-166 CH₂ Me H CH CMe S XLI-167 O Me H CH CMe S XLI-168 CHMe Me H CH CMe S XLI-169 CH₂ H H N CH NMe XLI-170 CHMe H H N CH NMe XLI-171 CHEt H H N CH NMe XLI-172 CHF H H N CH NMe XLI-173 C═CH₂ H H N CH NMe XLI-174 O H H N CH NMe XLI-175 S H H N CH NMe XLI-176 NH H H N CH NMe XLI-177 NMe H H N CH NMe XLI-178 NCHO H H N CH NMe XLI-179 NCOMe H H N CH NMe XLI-180 CH₂ Me H N CH NMe XLI-181 O Me H N CH NMe XLI-182 CHMe Me H N CH NMe XLI-183 CH₂ H H N CMe NMe XLI-184 CHMe H H N CMe NMe XLI-185 CHEt H H N CMe NMe XLI-186 CHF H H N CMe NMe XLI-187 C═CH₂ H H N CMe NMe XLI-188 O H H N CMe NMe XLI-189 S H H N CMe NMe XLI-190 NH H H N CMe NMe XLI-191 NMe H H N CMe NMe XLI-192 NCHO H H N CMe NMe XLI-193 NCOMe H H N CMe NMe XLI-194 CH₂ Me H N CMe NMe XLI-195 O Me H N CMe NMe XLI-196 CHMe Me H N CMe NMe XLI-197 CH₂ H H N CH O XLI-198 CHMe H H N CH O XLI-199 CHEt H H N CH O XLI-200 CHF H H N CH O XLI-201 C═CH₂ H H N CH O XLI-202 O H H N CH O XLI-203 S H H N CH O XLI-204 NH H H N CH O XLI-205 NMe H H N CH O XLI-206 NCHO H H N CH O XLI-207 NCOMe H H N CH O XLI-208 CH₂ Me H N CH O XLI-209 O Me H N CH O XLI-210 CHMe Me H N CH O XLI-211 CH₂ H H N CMe O XLI-212 CHMe H H N CMe O XLI-213 CHEt H H N CMe O XLI-214 CHF H H N CMe O XLI-215 C═CH₂ H H N CMe O XLI-216 O H H N CMe O XLI-217 S H H N CMe O XLI-218 NH H H N CMe O XLI-219 NMe H H N CMe O XLI-220 NCHO H H N CMe O XLI-221 NCOMe H H N CMe O XLI-222 CH₂ Me H N CMe O XLI-223 O Me H N CMe O XLI-224 CHMe Me H N CMe O XLI-225 CH₂ H H N CH S XLI-226 CHMe H H N CH S XLI-227 CHEt H H N CH S XLI-228 CHF H H N CH S XLI-229 C═CH₂ H H N CH S XLI-230 O H H N CH S XLI-231 S H H N CH S XLI-232 NH H H N CH S XLI-233 NMe H H N CH S XLI-234 NCHO H H N CH S XLI-235 NCOMe H H N CH S XLI-236 CH₂ Me H N CH S XLI-237 O Me H N CH S XLI-238 CHMe Me H N CH S XLI-239 CH₂ H H N CMe S XLI-240 CHMe H H N CMe S XLI-241 CHEt H H N CMe S XLI-242 CHF H H N CMe S XLI-243 C═CH₂ H H N CMe S XLI-244 O H H N CMe S XLI-245 S H H N CMe S XLI-246 NH H H N CMe S XLI-247 NMe H H N CMe S XLI-248 NCHO H H N CMe S XLI-249 NCOMe H H N CMe S XLI-250 CH₂ Me H N CMe S XLI-251 O Me H N CMe S XLI-252 CHMe Me H N CMe S XLI-253 CH₂ H H CH N NMe XLI-254 CHMe H H CH N NMe XLI-255 CHEt H H CH N NMe XLI-256 CHF H H CH N NMe XLI-257 C═CH₂ H H CH N NMe XLI-258 O H H CH N NMe XLI-259 S H H CH N NMe XLI-260 NH H H CH N NMe XLI-261 NMe H H CH N NMe XLI-262 NCHO H H CH N NMe XLI-263 NCOMe H H CH N NMe XLI-264 CH₂ Me H CH N NMe XLI-265 O Me H CH N NMe XLI-266 CHMe Me H CH N NMe XLI-267 CH₂ H H CMe N NMe XLI-268 CHMe H H CMe N NMe XLI-269 CHEt H H CMe N NMe XLI-270 CHF H H CMe N NMe XLI-271 C═CH₂ H H CMe N NMe XLI-272 O H H CMe N NMe XLI-273 S H H CMe N NMe XLI-274 NH H H CMe N NMe XLI-275 NMe H H CMe N NMe XLI-276 NCHO H H CMe N NMe XLI-277 NCOMe H H CMe N NMe XLI-278 CH₂ Me H CMe N NMe XLI-279 O Me H CMe N NMe XLI-280 CHMe Me H CMe N NMe XLI-281 CH₂ H H CH N O XLI-282 CHMe H H CH N O XLI-283 CHEt H H CH N O XLI-284 CHF H H CH N O XLI-285 C═CH₂ H H CH N O XLI-286 O H H CH N O XLI-287 S H H CH N O XLI-288 NH H H CH N O XLI-289 NMe H H CH N O XLI-290 NCHO H H CH N O XLI-291 NCOMe H H CH N O XLI-292 CH₂ Me H CH N O XLI-293 O Me H CH N O XLI-294 CHMe Me H CH N O XLI-295 CH₂ H H CMe N O XLI-296 CHMe H H CMe N O XLI-297 CHEt H H CMe N O XLI-298 CHF H H CMe N O XLI-299 C═CH₂ H H CMe N O XLI-300 O H H CMe N O XLI-301 S H H CMe N O XLI-302 NH H H CMe N O XLI-303 NMe H H CMe N O XLI-304 NCHO H H CMe N O XLI-305 NCOMe H H CMe N O XLI-306 CH₂ Me H CMe N O XLI-307 O Me H CMe N O XLI-308 CHMe Me H CMe N O XLI-309 CH₂ H H CH N S XLI-310 CHMe H H CH N S XLI-311 CHEt H H CH N S XLI-312 CHF H H CH N S XLI-313 C═CH₂ H H CH N S XLI-314 O H H CH N S XLI-315 S H H CH N S XLI-316 NH H H CH N S XLI-317 NMe H H CH N S XLI-318 NCHO H H CH N S XLI-319 NCOMe H H CH N S XLI-320 CH₂ Me H CH N S XLI-321 O Me H CH N S XLI-322 CHMe Me H CH N S XLI-323 CH₂ H H CMe N S XLI-324 CHMe H H CMe N S XLI-325 CHEt H H CMe N S XLI-326 CHF H H CMe N S XLI-327 C═CH₂ H H CMe N S XLI-328 O H H CMe N S XLI-329 S H H CMe N S XLI-330 NH H H CMe N S XLI-331 NMe H H CMe N S XLI-332 NCHO H H CMe N S XLI-333 NCOMe H H CMe N S XLI-334 CH₂ Me H CMe N S XLI-335 O Me H CMe N S XLI-336 CHMe Me H CMe N S

Table XLII provides 612 compounds of formula Iap

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and R⁹ are given in Table 3.

Table XLIII provides 612 compounds of formula Iaq

wherein the values of R¹, R², R^(4a), R^(4b), R^(4c), R^(4d), R⁵, R⁶ and given in Table 3.

The following tables provide characterising data for some of the compounds in Tables I-XLIII; other compounds are only described in these tables.

TABLE 1 Characterising Data

Cpd.No R1 Y R4a R4b R4c R4d Mp [° C.] 1.001 H CH₂ F H H F Solid 1.002 H CH₂ H H Br H 167-169 1.003 H CH₂ H H Cl H 164-166 1.004 H CH₂ H H Me H 156-157 1.005 H CH₂ F H F H 175-178 1.006 H CH₂ MeO H H MeO 163-165 1.007 H CH₂ Me H Me H 153-155 1.008 H CH₂ H H MeO H 159-161 1.009 H CH₂ H MeO H H 148-150 1.010 H CH₂ MeO H H H 178-179 1.011 H CH₂ H Me MeO H 141-143 1.012 H CHMe H H H H 112-115 1.013 Me CH₂ H H H H 166-168 1.014 H S H Me H H 234-235 1.015 H O H Me H H 133-134 1.016 H CH₂ OH H H H Decomp. 100 1.017 H CH₂ OCH2OMe H H H 171 1.018 H CH₂ H H H H 160 1.019 H O Cl H H H 185 1.020^(a)) Me CH₂ H H H H resin 1.021 H S H H H H resin R2, R7, R8, R9 = H ^(a))R2 = Me

TABLE 2 Characterising Data

Cpd.No R1 R2 R5 R6 R4a R4b R4c R4d Mp [° C.] 2.001^(a)) H H H H H H H H Solid 2.002 H H H H H H H H 137 2.003^(b)) H H H H H H H H 123 2.004^(c)) H H H H H H H H 123 2.005 H H H H H F H H 136 2.006 H H H H Me H H H 134 2.007 H H H H H H Me H 181 2.008 H H H H Br H H Me Solid 2.009 H H H H Me H H Br Solid 2.010 H H H H H H H OCH₂OMe Oil 2.011 H H H H OCH₂OMe H H H Solid 2.012 H H H H OH H H H 191 2.013 H H H H OTf H H H Resin 2.014 H H H H Et H H H Solid 2.015 H H H H OH H H H 125 Decomp. 2.016 H H H H H H H Me 117-120 2.017 H H H H H OCH₂OMe H H 150-153 2.018 H H H H OMe H H H Solid 2.019 H H H H F H H H 149 2.020 H H H H Cl H H H 124-127 2.021^(c)) H H H H Me H H H 119 2.022^(b)) H H H H Me H H H 122 2.023 H H H H F F H H 161 2.024 H H H H F H F H 145-152 2.025 H H H H F H H F 182 2.026 H H H H F H Br H 156 2.027 H H Me Me H H H H  60-66 2.028 H H H H F F F H 123 2.029 H H H H H OH H H 75 Decomp. 2.030 H H H H F H F F 172 2.031 H H H H F H Me H 184 2.032^(d)) Me H H H H H H H Solid 2.033 Me Me H H H H H H 119 2.034 Pr Pr H H H H H H 101-103 2.035 H H H H H Me OMe H 152-153 2.036 H H H H F F F F 165 2.037 H H H H F H Ph H Solid 2.038 H H H H F H Et H 148-149 2.039 H H H H COOMe H H H 131 2.040^(e)) H CH₂ H H H H H 173-175 2.041 H H H H PhO H H H 143-146 2.042 H H H H NO₂ H H H 144-145 2.043 H H H H (mCF₃)PhO H H H 115-116 2.044 H H H H CN H H H Resin 2.045 H H H H pClPhO H H H 163-164 2.046 H H H H I H H H 170-171 2.047 H H H H Me₃SiC≡C H H H Solid 2.048 H H H H HC≡C H H H Oil 2.048 H H OBn H F H F H Cis Oil 2.049 H H H H H H Br H solid 2.050 H H H H H H H Cl solid 2.051 H H H H H H H NHAc solid 2.052 H H H H H H H F 171-172 2.053 H H H H m-CF₃-phenyl H H H 103-105 2.054 H H H H PhCC— H H H 160-161 2.055 H H H H p-Cl-phenyl H H H 187-188 2.056 H H H H vinyl H H H solid 2.057 H H H H formyl H H H 142-143 2.058 H H H H CHF₂ H H H 116-117 2.059 H H H H MeOCH═N— H H H resin 2.060 H H N₃ H F H F H Cis Resin 2.061 H H SMe H F H F H Cis Resin 2.062 H H H H CCl₃ H H H Solid 2.063 H H NH₂ H F H F H Trans Resin 2.064 ═CH₂ H H H H H H 107-111 2.066 H —CH₂— H H H H H Exo124-129 2.067 F H H H F H H H Trans 142-144 2.068 H H SMe H SMe H F H Trans 143-149 2.069 F H S(O)Me H F H H H Cis solid 2.070 H H COOMe H H H H H Cis 105-107 ^(a))HCl salt ^(b))S-isomer ^(c))R-isomer ^(d))mixture of cis and trans ^(e))endo

TABLE 3 Characterising Data

Mp Cpd.No. Y CR9-CR1R2 R4a R4b R4c R4d [° C.] 3.002 0 CH—CF2 Me H H H 162 3.004 CH₂ CMe—CH2 H H H H a) a)¹H-NMR (300 MHz CDCl₃) 1.68 (3H, s, Me); 2.18 (1H, m); 2.73 (1H, m); 2.88 (1H, m); 3.03 (1H, m); 3.22 (2H, t); 3.98 (2H, m); 7.27 (4H, m).

TABLE 4 Characterising Data

Cpd.No. Td Te Tf R7 R8 Mp 4.001 S CH CH H H 147-149 4.002 NMe CH H H H 154-156 4.003 O N CMe H H 141-143 4.004 O CMe CH H H 148-150 4.005 O CMe CH Me Me  87-89 4.006 O CH CH Me Me resin

Characterising Data-5

Cpd. Phys. No. Ta Tb Tc Td Y R10 Data 5.001 N CMe N CH CH₂CH₂ H Oil 5.002 N C—CF₃ CH CH CH₂ H solid 5.003 N C—CHF₂ CH CH CH₂CH₂ H solid 5.004 N C—CF₃ CH CH CH₂CMe₂ H  74-75 5.005 N CH CH CH CH₂ H solid 5.006 N C—CF₃ CH CH CH₂ CN solid 5.007 N C—CF₃ CH CH CH₂ Boc 144-147

TABLE 6 Characterising Data

Cpd.No. R1 R2 Y R4a R4b R4c R4d Isomer Mp [° C.] 6.001 H H C═O H H H H 145-147 6.002 F F CHF H H H H a) 6.003 H H CH₂ H H H Et  98-100 6.004 H H CHOH F H F H cis 167 6.005 H H SO₂ H H H H 164-166 6.006 H H CH₂ H Br H H 137-139 6.007 H H CH₂ OCHF₂ H H H Oil 6.008 H H CH₂ OCSNMe₂ H H H Resin 6.009 Me H CH₂ H H H H trans 122 6.010 H H CHOH H H H H trans 149 6.011 H H CH₂ H H H nPr  72-75 6.012 Me H CH₂ H H H H cis Solid 6.013 iPr H CH₂ H H H H cis Solid 6.014 H H CH₂ COOBu H H H Resin 6.015 Et H CH₂ H H H H cis Solid 6.016 Et H CH₂ H H H H trans Solid 6.017 H H CHEt H H H H 1:5 c:t brown solid 6.018 H H CHiPr H H H H 1:1 c:t oil 6.019 H H CHMe H H H H cis 126 6.020 H H CHMe H H H H 1:3 c:t 139 6.021 H H C═O F H F H 144-155 6.022 F H H F H H H cis 159 6.023 H H CHF F H F H trans brown crystals 6.024 H H CHF F H F H cis brown crystals 6.025 COOBu H CH₂ H H H H trans  99-109 6.026 COOMe H CH₂ H H H H trans yellow oil 6.027 CH₂OH H CH₂ H H H H cis 147-148 6.028 COONa H CH₂ H H H H cis >200 6.029 CONHBn H CH₂ H H H H cis 194-198 6.030 H H CHOMe F H F H cis 115-116 6.031 H H O H H H H 135-156 6.032 OH H CH₂ H H H H trans 182-202 6.033 H H CH₂ H H H OTf brown resin 6.034 H H O CH₃ H H H 137-138 6.035 H H O H H F H 107-108 6.036 H H O OMe H H H 144-144 6.037 H H O Cl H H H 150-151 6.038 H H O Cl H Cl H b) 6.039 H H O CHF₂ H H H 130-131 6.040 H H O H F H H 113-114 6.041 H H NC(O)Me H H H H 160-161 a)¹H-NMR (300 MHz, CDCl₃) 3.39 (2H, t); 3.98 (2H, m); 5.44 (1H, t, J = 8); 5.79 (1H, ddd, J = 49, 8, 6); 7.50 4H, m). b)¹H-NMR (300 MHz CDCl₃) 3.34 (2H, t); 3.88 (2H, m); 4.38 (NH, b), 4.52 (1H, m); 4.80 (1H, m), 5.40 (1H, m), 7.24 (4H, m).

TABLE 7 Characterising Data

Cpd.No R1 R5 R4a R4c R4d R¹⁰ isomer Mp [° C.] 7.001 H H Cl H H OH 115-117 7.002 H H H H H NHBoc  63-64 7.003 H H H H H N═CMe₂ oil 7.004 H H H H H N(Ac)₂  91-92 7.005 H H H H H NHAc solid 7.006 H H F H H OH 142-143 7.007 H H H H H OH white crystals 7.008 H Me H H H OH cis 178-179 7.009 H Me H H H OH trans white crystals 7.010 H H Me H H OH 183 7.011 H H H H H Me orange oil 7.012 H H H H H OMe orange oil 7.013 H H H H H NH₂ 103-105

TABLE 8 Characterising Data

Cpd.No R1 R2 Y R4a R4c R4d R¹⁰ isomer Mp [° C.] 8.001 H H CH₂ Br H Me 2-thiazolyl white solid 8.002 H H CH₂ Me H Br 2-thiazolyl 176-181 8.003 H H O H H H 2-thiazolyl beige crystals 8.004 H H CHMe H H H Boc 187-8 8.005 H H CHMe H H H thexylMe₂Si orange solid 8.006 H H CHMe H H H iPr₃Si solid 8.007 Me Me CH₂ H H H 2-thiazolyl 162-3 8.008 H H CH₂ H H Et 2-thiazolyl 111 8.009 H H CH₂ H H Me 2-thiazolyl 125 8.010 H H C═O F F H 2-thiazolyl 150-162 8.011 H H C═O H H H 2-thiazolyl 188 8.012 H H CHOH F F H 2-thiazolyl white foam 8.013 H H CH₂ F H H 2-thiazolyl 152-3 8.014 iPr H CH₂ H H H Boc cis oil 8.015 H H CH₂ m(CF₃)PhO H H CN resin 8.016 H H CH₂ I H H Boc oil 8.017 H H CH₂ H H H CN  90-91 8.018 H H CH₂ F H H CN  99-100 8.019 H H CH₂ OCHF₂ H H CN resin 8.020 H H CHOBoc F F H Me Cis 101-105 8.021 H H CHOH F F H Me Cis 170-173 8.022 H H CHOH F F H Boc Cis 119 8.023 H H C═O F F H Boc 158 8.024 H H CH₂ OCHF₂ H H CN solid 8.025 H H CH₂ F H H acetyl solid 8.026 H H CH₂ Me H H CN resin 8.027 H H CH₂ NO₂ H H CN solid 8.028 H H CH₂ 3-CF₃-phenyl H H CN resin 8.029 H H CH₂ PhCC H H CN solid 8.030 H H CH₂ I H H CN solid 8.031 H H CH₂ Me H H acetyl resin 8.032 H H CH₂ CHF₂ H H CN solid 8.033 H H CH₂ H H H Me₂NCO— resin 8.034 H H CH₂ F H H Me₂NCO resin 8.035 H H CH₂ I H H MeOCH₂ oil

Characterising Data-9

Mp [° C.] or Cpd. retention No. Y R4a R4c Isomer time^(a) 9.001 CHOC(CF₃)Ph₂ F F cis  96-103 9.002 C═NOiBu F F 0.85 9.003 C═NOCH₂(2,4,5-Cl₃Ph) F F 1.27 9.004 C═NOBn F F 0.95 9.005 C═NNHC(O)(1-Me-3-CF₃- pyrazol-4-yl) F F 0.47 9.006 C═NNHC(O)NHPh F F 0.92 9.007 C═NO-allyl F F 0.43 9.008 C═NNHC(O)OPh F F 0.43 9.009 C═NNHSO₂Ph F F 0.79 9.010 C═NOtBu F F 1.00 9.011 C═NNHC(O)(benzo[1,2,5] thiadiazole-5-yl) F F 0.31 9.012 C═NO-pentafluorophenyl F F 1.13 9.013 C═NNHC(S)NHiPr F F 0.83 9.014 C═NNHSO₂Me F F 0.17 9.015 C═NNHC(S)NHMe F F 0.18 9.016 C═NNHC(O)(2-benzylthio- phenyl) F F 1.01 9.017 C═NOnBu F F 0.91 9.018 C═NNHTroc F F 0.85 9.019 C═NOEt F F 0.25 9.020 C═CH₂ F F Solid 9.021 C═CF₂ H H 106-108 9.022 C═NOH F F Decomp. 155 9.023 C═NOMe F F 104-114 ^(a)On a Waters 2795 HPLC using an Atlantis dC18 3ym, 3 x 20 mm column two mobile phases were used. Eluant A contained 90% water, 10% MeCN, 0.1% formic acid. Eluant B contained 0.1% formic acid in MeCN. For the first 2.5 min a linear gradient change of eluant was made from 90% eluant A/10% eluant B to 100% eluant B. Then 100% eluant B was used. The flow rate was 1.7 ml/min throughout. Compounds were detected by UV at using a diode array measuring wavelengths between 200 nm and 400 nm.

Characterising Data-10

retention Cpd.No R¹⁰ time^(a) 10.001 C(O)(2,5-dimethyl-furan-3-yl) 1.02 10.002 C(O)(1,3-dimethyl-pyrazol-5-yl) 1.05 10.003 C(O)CH₂OBn 1.58 10.004 C(O)OnBu 0.78 10.005 C(O)NEt₂ 0.42 10.006 C(O)iPr 0.70 10.007 C(O)NPh₂ 1.28 10.008 C(O)n-heptyl 1.57 10.009 C(O)-2-furyl 0.63 10.010 C(O)CH═CH(p-nitrophenyl) 1.69 10.011 C(O)Et 0.36 10.012 C(O)OPh 0.81 10.013 C(O)cyclopropyl 0.39 10.014 C(O)Ph 1.15 10.015 C(O)OMe 0.18 10.016 C(O)-1-piperidyl 0.70 10.017 C(O)-3,5-dimethyl-isoxazol-4-yl 1.47 10.018 C(O)isopropenyl 0.27 10.019 C(O)—O-isopropenyl 0.33 10.020 C(O)OEt 0.49 10.021 C(O)CH₂C(O)OEt 1.56 10.022 C(O)CH₂-2-thienyl 1.33 10.023 benzyl Oil 10.024 CH₂OMe Oil 10.025 C(O)Me 86-97 10.026 3-methoxybenzyl Oil ^(a)On a Waters 2795 HPLC using an Atlantis dC18 3ym, 3 x 20 mm column two mobile phases were used. Eluant A contained 90% water, 10% MeCN, 0.1% formic acid. Eluant B contained 0.1% formic acid in MeCN. For the first 2.5 min a linear gradient change of eluant was made from 90% eluant A /10% eluant B to 100% eluant B. Then 100% eluant B was used. The flow rate was 1.7 ml/min throughout. Compounds were detected by UV at using a diode array measuring wavelengths between 200 nm and 400 nm.

Characterising Data-11

Cpd.No Td Te Tf Y R₁ R₂ R₁₀ Mp [° C.] 11.001 S CH CH CH₂ H H H 144-145 11.002 S CH CH CH₂ H H CH₂C≡CH a) 11.003 CH CH S CH₂ H H H 146-147 11.004 S CMe CH CH₂ H H H 170-172 11.005 S CH CH CH₂ H H C(O)NM2₂ b) a)¹H-NMR (300 MHz CDCl₃) 2.21 (1H, t), 2.38 (1H, m), 2.83 (2H, m), 3.03 (1H, m), 3.32 (2H, m); 3.56 (2H, m), 4.16 (2H, m); 4.56 (1H, m), 6,83 (1H, d), 7.13 (1H, d). b)¹H-NMR (300 MHz CDCl₃) 2.38 (1H, m), 2.82 (2H, m), 2.90 (6H, S), 3.02 (1H, m), 3.20 (2H, m); 3.80 (2H, m), 4.16 (2H, m); 4.53 (1H, m), 6,82 (1H, d), 7.13 (1H, d).

Characterising Data-12

Cpd.No R1 Mp [° C.] 12.001 nBu Cis 91-94 12.002 nBu Trans 80-82 12.003 COnPr Cis 105-106 12.004 F Cis Resin 12.005 C(O)Me Cis 128-129 12.006 C(O)Et Cis 104-105 12.007 CH₂OH Trans144-145 12.008 OAc Trans Oil 12.009 CH₂OAc Trans Resin 12.010 OMe Trans 96-98 12.011 OBz Trans 117-119 12.012 CH₂OMe Trans Resin 12.013 CH₂OMs Trans Solid 12.014 CH₂OBn Trans 140 Decomp. 12.015 CH₂SMe trans resin 12.016 CH₂Ocinnamyl Trans Oil 12.017 CH₂OCH₂CO₂tBu Trans Oil 12.018 CH₂S(O)Me trans resin 12.019 CH₂SO₂Me trans resin 12.020 SePh Trans Oil 12.021^(g)) CH₂SH Trans 141-147 12.022 CH₂SePH Trans 99-101 12.023 CH₂SC(S)NEt₂ Trans Resin 12.024 CH₂CN Trans 110-113 12.025 CH₂SCN Trans Oil 12.026 CH₂OpFPh Trans 127-133 12.027 CH₂OPh Trans 100 Decomp. 12.028 CH₂SC(S)OEt Trans Resin 12.029 CO₂H trans solid ^(g))TFA salt

The compounds of the invention may be made by a variety of methods, for example those described in Tet. 2006, 62, 513

The compounds of the formula I can be prepared from amines of the formula II.

Methods for performing this transformation include A. Treatment with haloethylisothiocyanate as used in Examples 3, 8 (step 6) and 9 (step 6) using the procedures of for example DE 3133918, Indian J. Chem. 1984, 23B, 1243-57 or Heterocycles 1990, 30, 463-9; and B. Treatment with 2-methylthio-2-thiazoline as described in Example 1 following the procedures in for example J. Am. Chem. Soc. 1958, 80, 3339, J. Org. Chem. 1961, 26, 1666 or J. Med. Chem. 1982, 25, 735-42.

In a further aspect of the invention there is provided the use of 2-alkoxy-2-thiazolines, or 2-aryloxy-2-thiazolines of the formula (III)

where R_(z) is optionally substituted alkyl and aryl as reagents for the preparation of compounds of formula I. The transformation using III is described in Examples 2 and 4. The use of these reagents offers considerable advantages over the use of the corresponding 2-methylthio-2-thiazoline (see Example 3), as the reaction takes place at lower temperature (see Examples 2 and 4).

Additional methods for converting amines into aminothiazolines are described in the literature and can be adapted for transforming amines (II) into aminothiazolines (I). Thus the amines can be converted to thioureas and then treated with 1,2-dibromoethane as described in for example J. Het. Chem. 1986, 23, 1439-42, or also in Ind. J. Chem 1983, 22B, 249-51, or the amines can be treated at higher temperature with an 2-amino-thiazoline following the method of CH 667652.

Alternatively the amines can be converted to thioureas and then treated with 2-bromo-ethylamine as described in Bioorg. Med. Chem. 2001, 9, 2025.

As a further alternative the amines (II) can be converted into isothiocyanates (VI) and then treated with 2-halo-ethylamine as described in for example J. Org. Chem. 1983, 48, 3901-8 or also in J. Med. Chem. 1987, 30, 1955-62.

The amines (II_(i)) can be used to make 2-hydroxyethyl-thioureas (VII_(i)), according to methods found in Houben-Weyl E4, (1983) 484, for example using in a first step thiophosgene, and then in a second step 2-hydroxyethylamine. The thioureas (VII_(ii)) can be prepared from the isothiocyanates (VI) as described in Example 11. Each of these thioureas can be cyclised to the corresponding thiazolines (I), for example with acid as described for example in U.S. Pat. No. 4,398,028 and in Tet. Lett. 2003, 44, 795-9, or with Ph₃P and DEAD as described in Tet. Lett. 1999, 40, 3125 and also described in Example 11. If R¹⁰ is H, then (II) and (II_(i)) are identical, (VII₁) and VII_(ii)) are identical, and (I_(i)), (I_(ii)) and (Iiii) are tautomers of the same compound.

The amines (II) can be converted into isothiocyanates (VI) and then treated with aziridine to the corresponding thioureas which can then be rearranged to the aminothiazolines as described for example in Arch. Pharm. 1958, 291, 457 or also in J. Amer. Chem. Soc. 1961, 83, 2570.

Compounds of the formula I and R⁹ and R¹⁰ are H can be prepared from ketones of the formula IV.

Thus the ketone and 2-aminothiazoline are treated with an agent, which adsorbs, absorbs, or reacts with water such as titanium tetraalkoxide to yield an imine or enamine intermediate, which is then treated with a reducing agent such as sodium borohydride to yield the aminothiazoline (I). An example of this method is described in Example 8. The reaction of ketones with primary amines using drying and reducing agents to form secondary amines is known as reductive amination and is described in for example Organic Reactions 2002, 59, 1-714.

Compounds of the formula I where R¹⁰ is not H can be prepared from compounds of the formula I where R¹⁰ is hydrogen, by treatment with a suitable derivatising agent. When R¹⁰ is an acyl group, acylating agents can be used. When R¹⁰ is an alkyl group, alkylating agents can be used. When R¹⁰ is a sulfenyl group, sulfenylating agents can be used. Derivatisation is this manner is well known. Descriptions and methods for these transformations can be found in T. W. Greene and P. G. M. Wuts “Protective Groups in Organic Synthesis” 3^(rd) Edition, Wiley, N.Y., 1999. The group R¹⁰ can also be introduced via a synthetic precursor of compounds of the formula I, for example via an amine of the formula II_(i), or via a N—R¹⁰ substituted hydroxyethylamine.

Amines of the formula (II) can be prepared in various ways. Thus ketones (IV) can be converted into amines of the formula (II) wherein R⁹ is H. One method for this transformation involves reductive amination for example according to Example 7 and Tetrahedron 2004, 60, 1463-71. This transformation can also be performed in two steps via an oxime and subsequent reduction as exemplified in Examples 9 and intermediate example 1.

Amines of the formula (II) can also be prepared from carboxylic acids (V), by a Curtius degradation as shown in Example 5.

Amines of formula (II), wherein Y is oxygen are partially known or may be prepared by the known methods as described in Chimica Acta Turica, 13(3), 403-412 (1985) and Farmaco, Edizione Scientifica, 43(7-8), 643-655 (1988).

Certain of the isothiocyanates of the formula (VI) are new and are part of this invention.

The novel compounds are those of the formula VIA

where R₁, R₄a, R₄b, R₄c and R₄d are each independently H, halogen, C₁-C₆ alkyl or C₁-C₆ haloalkyl, and where at least one of these substituent must be different to H.

Preferred compounds of the formula (VIA) are those wherein the values R₁, R₄a, R₄b, R₄c and R₄d are given in Table 9.

TABLE 9 Compound No R1 R₄a R₄b R₄c R₄d VIA-1 H F H H H VIA-2 H CH₃ H H H VIA-3 H F H F H VIA-4 H F H CH₃ H VIA-5 H F H H F VIA-6 H CH₃ H F H VIA-7 F H H H H VIA-8 CH₃ H H H H VIA-9 F F H H H VIA-10 F CH₃ H H H VIA-11 F F H F H VIA-12 F F H CH₃ H VIA-13 F F H H F VIA-14 CH₃ F H H H VIA-15 CH₃ CH₃ H H H VIA-16 CH₃ F H F H VIA-17 CH₃ F H CH₃ H VIA-18 CH₃ F H H F

The compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).

Examples of pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides fells (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), and Deroceras reticulatum (slug).

The invention therefore provides a method of combating and controlling insects, acarines, or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, The compounds of formula (I) are preferably used against insects or acarines.

The term “plant” as used herein includes seedlings, bushes and trees.

In order to apply a compound of formula (I) as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of pests such that a compound of formula (I) is applied at a rate of from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kg per hectare, more preferably from 1 g to 1 kg per hectare.

When used in a seed dressing, a compound of formula (I) is used at a rate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably 0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

In another aspect the present invention provides an insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal, acaricidal, nematicidal or molluscicidal composition.

In a still further aspect the invention provides a method of combating and controlling pests at a locus which comprises treating the pests or the locus of the pests with an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a composition comprising a compound of formula (I). The compounds of formula (I) are preferably used against insects, acarines or nematodes.

The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70° C.) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.

A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).

A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- and tri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.

Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

A compound of formula (I) may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.

A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.

A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I).

The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).

The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.

The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following:

a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl; d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron; e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin; f) Pyrazoles, such as tebufenpyrad and fenpyroximate; g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin; h) Hormones or pheromones; i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin; j) Amidines, such as chlordimeform or amitraz; k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam; l) Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam; m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide; n) Diphenyl ethers, such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; or q) Pymetrozine.

In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).

Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethyl-benzimidazole-1-sulphonamide, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH-7281, zoxamide), N-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON65500), N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1,1′-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propyl-5-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-A1, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb and ziram.

The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.

An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PIX™.

Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

The invention is illustrated by the following Examples:

Mass spectra data were obtained for selected compounds of the following examples using

LCMS: LC5: 254 nm—gradient 10% A to 100% B A=H₂O+0.01% HCOOH B=CH₃CN/CH₃OH+0.01% HCOOH positive electrospray 150-1000 M/z.

EXAMPLE 1

This Example illustrates the preparation of compound No 2.002

Example 1

A solution of 1-aminoindane (0.5 ml, 3.87 mmol), 2-methylthio-2-thiazoline (0.421 ml, 3.87 mmol), and methanesulfonic acid (0.251 ml, 3.87 mmol) in butanol (5 ml) was heated under reflux at 125° C. bath temperature for 16 hours. The solvent was evaporated, the crude product separated between HCl (2M) and diethyl ether. The organic phase was made basic with NaOH (32%) and the product extracted into dichloromethane, dried (MgSO₄) and evaporated to yield 912 mg of product as beige crystals m.p. 137° C.

EXAMPLE 2

This Example illustrates the preparation of compound No 2.002

A solution of 1-aminoindane (0.2 ml, 1.55 mmol), 2-methoxy-2-thiazoline (182 mg, 1.55 mmol), and methanesulfonic acid (0.050 ml, 0.77 mmol) in butanol (1 ml) was left at room temperature for 15 days. The mixture was shaken between NaOH (1M) and dichloromethane, and the organic phase dried (MgSO₄) and evaporated to yield 286 mg of product as beige crystals m.p. 137° C.

EXAMPLE 3

This Example illustrates the preparation of compound No 2.019

A solution of 4-fluoro-1-indanamine (300 mg, 1.98 mmol) in THF (2.5 ml) was stirred at 0° C. A solution of chloroethyl isothiocyanate (0.200 ml, 2.08 mmol) in THF (0.5 ml) was added, and the mixture stirred at room temperature overnight. The supernatant was decanted and the remaining crystals washed twice with ether, dissolved in water, basified with NaOH (32%) and the product extracted into dichloromethane, dried (MgSO₄) and evaporated to leave a dark yellow solid, which was washed twice with ether to yield the product as a fine white powder. m.p. 149° C.

EXAMPLE 4

This Example illustrates the preparation of compound number 6.011

A solution of 7-propyl-1-indanamine (184 mg, 1.05 mmol), 2-(p-tolyloxy)-2-thiazoline (0.174 ml, 203 mg, 1.05 mmol) and methansulfonic acid (0.034 ml, 50 mg, 0.527 mmol) in nBuOH (1 ml) was heated at 110° C. for 2 hours. The solvent was evaporated and the mixture shaken with tBuOMe, NaOH (2M) and NaCl (satd). The product was taken into HCl (2M), and after basification with NaOH (32%) back into tBuOMe, which was washed with NaCl (satd), dried (MgSO₄), and evaporated to yield 272 mg as a syrup, which crystallised on standing. m.p. 72-75° C.

EXAMPLE 5

This Example illustrates the preparation of compound number 3.004.

Step 1

A solution of indane-1-carboxylic acid (4.1 g, 25.3 mmol) in THF (30 ml) was added in portions to a solution of lithium diisopropylamide in THF (2M, 27.8 ml, 55.6 mmol) with stirring at −20° C. The solution was then stirred at 35° C. for 1 hour, then cooled again to −20° C. and a solution of methyl iodide (2.05 ml, 32.89 mmol) in THF (10 ml) was added. The light yellow solution was warmed at 35° C. for 4 hours before extracting between HCl (2M) and EtOAc to yield the crude product (4.5 g) as a brown oil. This mixture was cromatographed on HPLC with EtOAc/hexane to yield 1-methyl-1-indanecarboxylic acid (1 g) and recovered starting material (700 mg)

Step 2

A solution of 1-methyl-1-indanecarboxylic acid (864 mg, 4.9 mmol), diphenylphosphoryl azide (1.3 ml, 6.02 mmol) and triethylamine (0.95 ml, 6.87 mmol) in tBuOH (10 ml) was stirred with 5 g of 4A molecular sieves at 95° C. for 5 hours, while a gas was evolved. The mixture was cooled, diluted with EtOAc, filtered and the solvent evaporated. The crude product was redissolved in EtOAc, washed with water, dried with MgSO4, and evaporated to give the isocyanate as a brown oil (700 mg)

Step 3

The isocyanate from step 2 (300 mg, 1.73 mmol) was dissolved in THF (3 ml) and stirred with NaOH (2M, 2.4 ml) for 4 hours, then shaken between HCl (2M) and AcOEt. The aqueous phase was made basic with NaOH (conc.) and the product extracted into EtOAc, dried, and evaporated to give the amine (52 mg, 20%) as an oil.

Step 4

A solution of the amine from step 3 (110 mg, 0.748 mmol) in dichloromethane was added slowly to a stirred solution of thiophosgene (0.063 ml, 0.823 mmol) in dichloromethane (1 ml) and 103 mg potassium carbonate in water (1 ml)at 0° C. After 15 min a cold solution of KOH (1.496 mmol) in water (1 ml) was added and the mixture shaken between dichloromethane and water. The organic phase was dried and evaporated to give the isothiocyanate (90 mg) as an unstable oil.

Step 5

NaOH (2M, 0.237 ml) was added to a solution of 2-bromoethylamine hydrobromide (97 mg, 0.476 mmol) in water (0.1 ml) and stirred with ether (0.5 ml) at 0° C. A solution of the isothiocyanate from step 4 (90 mg, 0.476 mmol) in ether (1 ml) was added slowly and the mixture stirred at 0° C. for 30 minutes. The mixture was shaken between ether and water, and the ether phase extracted with HCl (2M). The aqueous phase was made basic with NaOH (2M) and the product extracted into EtOAc, which was dried and evaporated to yield 11 mg (10%) of the product. ¹H-NMR (300 MHz CDCl₃) 1.68 (3H, s); 2.18 (1H, m); 2.73 (1H, m); 2.88 (1H, m); 3.03 (1H, m); 3.22 (2H, t); 3.98 (2H, m); 7.27 (4H, m).

EXAMPLE 6

This Example illustrates the preparation of compound number 6.002.

Step 1.

Zinc dust (6 g) was washed with HCl (20% aq. 10 ml), then water, acetone and ether, then added to a solution of 2-bromobenzaldehyde (7.03 ml, 60.8 mmol) in THF (60 ml). Ethyl bromodifluoroacetate (9.5 ml, 73 mmol) in THF (30 ml) was added in portions. After the exothermic reaction was over the mixture was stirred for 3 hours, then shaken between EtOAc, NH₄Cl (sat.) and NaCl (sat.). The organic phase was dried and evaporated to yield the product (12 g) as a yellow oil.

Step 2.

A solution of the product from step 1 (12 g, 38.8 mmol) in dichloromethane (30 ml) was added slowly to a solution of DAST in dichloromethane (50 ml) at −70° C. After 30 minutes at this temperature it was allowed to warm to room temperature and stirred for 2 hours, then cooled and poured onto cooled NaHCO₃ (1M). The product was extracted into dichloromethane, dried and the solvent evaporated to yield the product (10 g) as a brown oil.

Step 3.

A solution of the product from step 2 (10 g, 32 mmol) in EtOH (200 ml) and NaOH (32%, 100 ml) was stirred at 90° C. for 5 hours, then cooled and shaken between ether and water. The aqueous phase was acidified with HCl (conc.) and the product extracted into ether, dried and evaporated to yield the acid (3.2 g) as a brown oil.

Step 4

A solution of BuLi in hexane (1.6 M, 1.47 ml, 2.36 mmol) was added slowly to a solution of the product from step 3 (304 mg, 1.07 mmol) at −10° C. After 10 minutes at this temperature it was warmed up to room temperature, poured onto HCl (2M aq.) and extracted into ether. The ether phase was dried and evaporated to yield 212 mg crude product, which was chromatographed on silica gel with 50% EtOAc/hexane to yield the 2,2,3-trifluoro-indanone (45 mg).

Step 5

A solution of 2,2,3-trifluoro-indanone (282 mg, 1.5 mmol), titanium isopropoxide (0.886 ml, 2.99 mmol) and ammonia (2M in EtOH, 2.5 ml) in EtOH was stirred for 5 hours. The mixture was cooled to 0° C. and NaBH4 (85 mg, 2.25 mmol) added. After stirring for 2 hours the mixture was left at room temperature overnight, then poured onto NH₄OH (25%, 10 ml) and extracted with EtOAc. The organic phase was washed with water, dried, and evaporated to yield the crude product (205 mg) as a brown oil. This was shaken between ether and HCl (2M aq.), basified with NaOH (2M) and extracted into ether. Evaporation yielded 1-amino-2,2,3-trifluoro-indane (90 mg) as an oil.

Step 6

Chloroethylisothiocyanate (0.045 ml, 0.470 mmol) was added to a solution of 1-amino-2,2,3-trifluoro-indane (80 mg, 0.427 mmol) in THF (0.5 ml). The white precipitate was filtered off to yield 40 mg of the product as an HCl salt. This was shaken between NaOH (aq.) and dichloromethane, the organic phase dried and evaporated to yield 31 mg of the product. ¹H-NMR (300 MHz, CDCl₃) 3.39 (2H, t); 3.98 (2H, m); 5.44 (1H, t, J=8); 5.79 (1H, ddd, J=49, 8, 6); 7.50 (4H, m).

EXAMPLE 7

This Example illustrates the preparation of compound number 6.002.

Step 1

A suspension of ammonium acetate (27.12 g, 351.8 mmol), malonic acid (18.31 g, 175.92 mmol) and 3,5-difluoro-benzaldehyde (25 g, 175.92 mmol) in ethanol (53 ml) was heated overnight under reflux, cooled to room temperature, the product filtered off, washed with ethanol and ether, and dried under vacuum to yield 21.07 g of product as a white powder.

Step 2.

TFAA (15 ml) was added to a solution of the product from step 1 (5 g, 24.85 mmol) in TFA (15 ml). After 45 minutes the mixture was poured onto 350 ml cold water and the product filtered off. It was washed with water and dried overnight in the air to yield 6.06 g of the trifluoroacetate as white crystals.

Step 3

Sulfuric acid (0.036 ml, 0.67 mmol) was added to a solution of the product from step 2 (2.0 g, 6.78 mmol) in TFA (10 ml) and TFAA (10 ml), and the mixture heated for 4 hours under reflux. The solvent was evaporated and the crude product stirred with ice/water (50 ml). The product was filtered off and washed with water and dried under vacuum to yield the indanone (1.48 g) as beige crystals.

Step 4.

Sodium borohydride (712 mg, 18.8 mmol) was added in portions to a suspension of the product from step 3 (5 g, 17.9 mmol) in MeOH (50 ml) at 0° C. After 2 hours at 0° C. acetic acid (0.5 ml) and water (2 ml) was added and the solvent evaporated. The crude product was taken up in dichloromethane, washed with HCl (1M) and NaHCO3 (sat.), dried and evaporated to give the product (4.87 g) as a mixture of cis and trans isomers. This mixture was stirred with a little ether and the pure cis isomer filtered off, washed with ether and dried to yield 2.48 g. Chromatography of the mother liquors on silica with 5% MeOH/dichloromethane led to the pure trans isomer (537 mg) as white crystals.

Step 5.

A solution of the cis isomer from step 4 (600 mg, 2.13 mmol) and potassium carbonate (1.47 g, 10.6 mmol) in methanol (20 ml) and water (4.5 ml) was heated under reflux for 2 hours, cooled and the solvent evaporated. The crude product was shaken between NaOH (2M) and dichloromethane. The organic phase was dried and evaporated to yield 160 mg product as brown crystals.

Step 6.

Chloroethylisothiocyanate (0.073 ml, 0.754 mmol) was added to a solution of the product from step 5 (133 mg, 0.718 mmol) in THF (3 ml), and the solution left overnight. The mixture was shaken between HCl (1M) and ether, the aqueous phase was basified with NaOH (32%), and the product extracted into dichloromethane, which was then dried and evaporated. The crude product was washed with ether (1×2 ml, and 2×0.5 ml) to yield the product (105 mg) as beige crystals. m.p. 167° C.

EXAMPLE 8

This Example illustrates the preparation of compound number 1.003

(7-Chloro-1,2,3,4-tetrahydro-naphthalen-1-yl)-(4,5-dihydro-thiazol-2-yl)-amine

Titanium isopropoxide (710 mg, 0.74 mls, 2.5 mmol) is added to a mixture of 7-chloro-1-tetralone (360 mg, 2 mmol) and 2-aminothiazoline (224 mg, 2.2 mmol). The reaction mixture is stirred for 16 hours at room temperature, then diluted with dry methanol (5 ml). Excess sodium borohydride is added carefully portionwise over a period of 45 minutes. The reaction mixture is stirred for a further 2 hours, then added to a saturated aqueous solution of Rochelle's salt and extracted with dichloromethane (2×25 mls). The organic phases are combined, washed sequentially with water and saturated brine, then filtered through a pad of magnesium sulphate. The filtrate is concentrated under reduced pressure to give the crude product as a pale yellow gum. The crude product is purified by column chromatography on silica, eluting with ethyl acetate to give the title compound as a white solid Mp 164-6° C. Nmr data: (CDCl₃): 7.39 (1H, s, CH), 7.13 (1H, dd, CH), 7.01 (1H, s, CH), 4.90 (1H, m, CH), 4.06 (2H, m), 3.37 (2H, m), 2.72 (2H, m), 2.08 (1H, m), 1.85 (3H, m)

EXAMPLE 9

This Example illustrates the preparation of compound number 1.014.

Step 1.

Hydroxylamine hydrochloride (590 mg, 8.4 mmol) was added in one portion to a stirring solution of ketone (1 g, 5.6 mmol) in methanol (15 ml) and the resultant yellow solution was stirred at room temperature for 16 hours. The reaction was then concentrated and triturated with ether and hexane to give a beige solid. This solid was collected and dried by filtration and NMR and MS confirmed this to be the desired oxime (0.802 g, 4.15 mmol, 74%).

Step 2.

Raney nickel (500 mg) was washed and added to a solution of oxime (532 mg, 2.8 mmol) in methanolic ammonia (7M, 10 ml). This suspension was then subjected to 3.85 bar hydrogen pressure at room temperature for 2.5 hours. The reaction was then filtered through hyflo and concentrated in vacuo to a light green solid. This solid was found by NMR to be the desired product (310 mg, 1.6 mmol, 57%) which was used crude in the next step.

Step 3.

1,1′-thiocarbonyldiimidazole (144 mg, 0.81 mmol) was added to a solution of amine (145 mmol, 0.81 mmol, slight presence of nickel) in DMF and stirred at room temperature for 16 hours. Ethyl acetate and water were then added and the organic phase washed with water and brine, dried (MgSO₄) and concentrated in vacuo. The crude orange oil was analysed by NMR, MS and IR, found to be desired isothiocyanate and was used immediately in the next step.

Step 4.

Triethylamine (0.15 ml, 1.1 mmol) was added to a suspension of 2-chloroethylamine hydrochloride (130 mg, 1.1 mmol) in DCM and the solution was stirred for 30 mins. Isothiocyanate (1.1 mmol) in DCM was then added. A GCMS was taken after an hour and showed the presence of desired product and SM. The reaction was stirred overnight. GCMS showed complete reaction and the solvent was removed in vacuo to give a crude orange solid. This was recrystallised from ethanol to give the product as a white solid (crop 1, 31 mg, 0.117 mmol, 14%) and a second crop as a beige solid (21 mg, 0.08 mmol, 10%). Overall yield for two steps 24%. m.p. 234-235° C.

EXAMPLE 10

This Example illustrates the preparation of Compound No 8.017

A suspension of 0.70 g (3.2 mmol) (4,5-Dihydro-thiazol-2-yl)-indan-1-yl-amine, 0.52 g (4.8 mmol) cyanogen bromide and 1.56 g (4.8 mmol) CsCO₃ in 10 ml acetonitrile—was stirred at 20° C. for 16 hours. The suspension was filtered and the solvent evaporated. The crude product was purified by flash chromatography using EtOAc/n-hexane (1:5) as eluent to yield 0.50 g of 2-(Indan-1-ylimino)-thiazolidine-3-carbonitrile (white crystals, m.p. 90-91° C.). ¹H-NMR (400 MHz, CDCl₃): 2.0-2.15 (1H, m); 2.40-2.50 (1H, m); 2.85-2.95 (1H, m); 3.0-3.10 (1H, m); 3.35-3.45 (2H, m), 3.90-4.0 (2H, m), 4.65 (1H, t), 7.10-7.30 (4H, m).

EXAMPLE 11

This example illustrates the preparation of compound 2.006

Step 1.

15.0 g (102.6 mmol) 4-methyl-indan-1-one is dissolved in 125 ml MeOH. The solution is cooled to 0-5° C. and 4.3 g (112.9 mmol) NaBH₄ is added portionwise while maintaining the temperature between 0-8° C. After the addition of NaBH₄ the cool-bath is removed and the reaction mixture is stirred till TLC indicates completion of the reaction. The reaction mixture is poured into water and extracted three times with EtOAc. The collected organic layers are washed with water and brine, dried over MgSO₄ and filtered. After evaporation of EtOAc 4-methyl-indan-1-ol is isolated in 98% yield. The crude material may be used directly without further purification.

¹H-NMR (ppm, CDCl₃): 1.95-2.03 (m, 1H); 2.30 (s, 3H); 2.45-2.55 (m, 1H); 2.70-2.80 (m, 1H); 2.95-3.05 (m, 1H); 5.25-5.30 (dd, 1H); 7.12 (d, 1H); 7.18 (t, 1H); 7.28 (d, 1H).

Step 2.

4.34 g (29.28 mmol) 4-methyl-indan-1-ol and 7.8 ml (35.14 mmol) diphenylphosphoryl azide are dissolved in dry THF at room temperature under argon. To this mixture is added slowly 5.0 ml (35.14 mmol) 1,8-diazabicyclo[5.4.0]undec-7-ene. The reaction is stirred for 6 h at room temperature (TLC monitoring). Then the mixture is poured into water and extracted three times with toluene. The organic layers are combined, dried over MgSO₄ and concentrated in vacuo. Purification using silica gel chromatography (hexane/EtOAc 9:1) affords pure 1-azido-4-methyl-indane as light orange liquid.

¹H-NMR (ppm, CDCl₃): 2.05-2.15 (m, 1H); 2.25 (s, 3H); 2.35-2.45 (m, 1H); 2.72-3.02 (m, 1H); 4.82-4.88 (dd, 1H); 7.10 (d, 1H); 7.15 (t, 1H); 7.22 (d, 1H).

Step 3.

1.0 g (5.8 mmol) 1-azido-4-methyl-indane is treated with 4.54 g (17.3 mmol) triphenylphosphine in 26 ml THF and 1.4 ml H₂O at room temperature overnight. Completion of the reaction is achieved by heating up the mixture for additional 2.5 hours. The reaction mixture is then cooled to room temperature and diluted with water. The pH is adjusted to 2 by adding cold (ca 0° C.) aqueous HCl (1M). After extraction with EtOAc the aqueous layer is separated, basified with NaOH (2M) and extracted into EtOAc. The organic layer is then dried (MgSO₄) and concentrated in vacuo to give 4-methyl-indan-1-yl-amine as a light yellow liquid.

¹H-NMR (ppm, CDCl₃): 1.55 (br s, 1H); 1.60-1.70 (m, 1H); 2.25 (s, 3H); 2.45-2.52 (m, 1H); 2.62-2.72 (m, 1H); 2.85-2.94 (m, 1H); 4.33 (t, 1H); 6.98-7.05 (m, 1H); 7.10-7.15 (m, 2H).

Step 4.

A mixture of 0.36 ml (4.32 mmol) thiophosgene in 4 ml dichloromethane is cooled to 0° C. after which a cold (0° C.) solution of 0.5 g (3.60 mmol) K₂CO₃ in 4 ml water is added. The mixture is stirred for 10 min and 0.53 g (3.60 mmol) indan-1-ylamine is then added drop wise with vigorous stirring at 0° C. After an additional 10 min a cold solution of 0.40 g (7.20 mmol) KOH in 4 ml water is added in one portion with cooling. The organic layer and three extracts (Et₂O) are combined, dried over MgSO₄, filtered and concentrated to give 1-isothiocyanato-4-methyl-indane as an orange brown liquid. The product is used directly without further purification.

¹H-NMR (ppm, CDCl₃): 2.18-2.28 (m, 1H); 2.28 (s, 3H); 2.50-2.60 (m, 1H); 2.75-2.85 (m, 1H); 2.95-3.05 (m, 1H); 5.19 (t, 1H), 7.11 (d, 1H); 7.18 (t, 1H); 7.25 (d, 1H).

Step 5.

680 mg (3.59 mmol) 1-isothiocyanato-4-methyl-indane is dissolved in 13 ml THF at room temperature under argon. Then 0.21 ml (3.59 mmol) 2-amino-ethanol is added slowly. The reaction mixture is stirred at room temperature overnight. After completion of the reaction as indicated by TLC the solvent is removed under reduced pressure to give the crude product. Subsequent purification by column chromatography on silica gel (CH₂Cl₂/MeOH 15:1) and stirring in Et₂O affords the title compound 1-(2-hydroxy-ethyl)-3-(4-methyl-indan-1-yl)-thiourea as a white powder (Mp 90-93° C.).

¹H-NMR (ppm, CDCl₃): 1.85-1.95 (m, 1H); 2.25 (s, 3H); 2.55 (br s, 1H); 2.60-2.70 (m, 1H); 2.71-2.81 (m, 1H); 2.86-2.99 (m, 1H); 3.62 (br s, 2H); 3.78 (t, 2H); 5.67 (br s, 1H); 6.47 (br s, 1H), 6.11 (br s, 1H); 7.07 (d, 1H); 7.12 (t, 1H); 7.18 (d, 1H).

Step 6.

500 mg (2.0 mmol) 1-(2-Hydroxy-ethyl)-3-(4-methyl-indan-1-yl)-thiourea and 786 mg (3.0 mmol) triphenylphosphine (TPP) were solved in 25 ml dry tetrahydrofuran (THF) at room temperature under Argon. After 15 minute stirring at 20° C. a solution of 606 mg (3.0 mmol) disopropyl azodicarboxylate (DIAD) in 10 ml THF was added drop wise while maintaining the temperature below 20° C. The reaction was complete after 3 hours indicated by TLC. Then the reaction mixture was concentrated under vacuo and 1 M HCl and ethyl acetate were added. The water layer was separated and three times extracted with ethyl acetate. The ph of the water phase was then adjusted to ca 8-9 by adding solid NaOH. The crude product was extracted into CH₂Cl₂ and thoroughly washed with water and brine. After drying over MgSO₄ and evaporation 428 mg (4,5-Dihydro-thiazol-2-yl)-(4-methyl-indan-1-yl)-amine were obtained as a white powder (Mp. 135-135° C.).

¹H-NMR (CDCl₃, ppm): 1.80-1.90 (m, 1H), 2.1.9 (s, 3H), 2.51-2.61 (m, 1H), 2.61-2.72 (m, 1H), 2.80-2.90 (m, 1H), 3.30 (t, 2H), 3.92-4.05 (m, 2H), 5.18 (t, 1H), 6.99 (d, 1H), 7.08 (t, 1H), 7.15 (d, 1H).

INTERMEDIATE EXAMPLE 1

This Example illustrates the preparation of 4,5-difluoro-1-indanamine.

Step 1 (According to G Toth et al. Synth. Comm. 1995, 25(19), 3067-74)

Triethylamine (30 ml) was added dropwise with stirring to formic acid (19 ml) at 0° C. To this solution was added 2,3-difluorobenzaldehyde (25 g, 176 mmol) and Meldrum's acid (25.4 g, 176 mmol) and the mixture heated at 100° C. for 2 hours, during which time gas evolved and 5 ml distillate was collected. The mixture was heated for a further 2 hours, then treated with ice/water (140 ml), and HCl (conc. aq.) to pH 1-2. The mixture was left at 5° C. overnight, and the product then filtered off, washed with water, dried first in the air then on the vacuum to yield 29.11 g white crystals of the (2,3-difluoro)-3-propionic acid.

Step 2

Thionyl chloride (6.43 ml, 88.64 mmol) was added to a suspension of (2,3-difluoro)-3-propionic acid (15 g, 80.58 mmol) in DMF (0.17 ml) and hexane (60 ml) with stirring. After stirring for one hour at room temperature the brown solution was heated at 50° C. for 2 hours then the solvent evaporated leaving the acid chloride as a brown oil. This was dissolved in dichloromethane (60 ml), AlCl₃ was added in three portions with stirring, and the dark brown/black mixture stirred overnight at room temperature. The mixture was poured onto ice/water, acidified with HCl (conc. 15 ml) and the product extracted into dichloromethane, which was washed with HCl (2M) and NaOH (2M), dried (MgSO₄), and evaporated to yield 7.21 g 4,5-difluoro-1-indanone as a brown solid (m.p. 28-32° C.).

Step 3

4,5-difluoro-1-indanone (5.0 g, 35.68 mmol) and hydroxylamine hydrochloride (3.72 g, 53.52 mmol) were dissolved in pyridine (16 ml) and the dark brown solution left at room temperature overnight, then poured onto 40 ml of ice/water. The product was filtered off, washed with water, and dried first in the air then under vacuum to yield 6.21 g of the oxime as a light beige powder.

Step 4

Sodium borohydride (4.34 g, 114.6 mmol) was added to a solution of TiCl₄ (6.3 ml, 57.3 mmol) in DME (120 ml) at 0° C. under stirring. A gas evolved, the temperature rose to 20° C., and the solution became light blue. After cooling to 0° C. a suspension of the oxime from step 3 (5.0 g, 27.3 mmol) in DME (20 ml) was poured in. The temperature rose to 20° C. and the mixture was stirred at room temperature overnight. The dark blue suspension was added in portions to a mixture of potassium tartrate (200 mmol), water (100 ml), and NaOH (32%, 50 ml), which was stirred at 0° C. This quenching was exothermic. After stirring for 2 hours the opalescent mixture was extracted with diethyl ether. The product was then extracted into HCl (1M), washed with ether, and after basifying with NaOH (32%), it was extracted into dichloromethane, which was dried and evaporated to yield 1.5 g of 4,5-difluoro-1-aminoindane as a light brown oil. ¹H-NMR (300 MHz, CDCl₃) 1.57 (3H, s, NH₂); 1.78 (1H, m); 2.57 (1H, m); 2.81 (1H, m); 3.09 (1H, m); 4.37 (1H, t) 7.00 (2H, m).

INTERMEDIATE EXAMPLE 2

This Example illustrates the preparation of dimethyl-thiocarbamic acid O-(1-oxo-indan-4-yl) ester

13.3 g (87 mmol) 4-hydroxy-indan-1-one was added portion wise to a suspension of 2.3 g (91.3 mmol) NaH in 200 ml dry DMF and stirred at 20° C. After hydrogen evolution had ceased, a solution of 11.8 g (95.6 mmol) N,N′-dimethylthiocarbamoyl chloride in 50 ml dry DMF was slowly added. The resulting mixture was stirred overnight at 20° C. After completion of the reaction indicated by TLC the reaction mixture was poured into ice water and extracted several times with EtOAc. The organic extract was thoroughly washed with 10% aq K2CO3, dried over MgSO4, and evaporated to dryness in vacuo. The crude product was purified by flash chromatography (hexane/EtOAc 3:1) to give 13.3 g (65%) of dimethyl-thiocarbamic acid O-(1-oxo-indan-4-yl) ester as a slight yellow solid compound. 1H-NMR (ppm, CDCl3): 2.65-2.7 (m, 2H), 3.05-3.1 (m, 2H), 3.4 (s, 3H), 3.5 (s, 3H), 7.25 (d, 1H), 7.4 (t, 1H), 7.7 (d, 1H).

INTERMEDIATE EXAMPLE 3

This Example illustrates the preparation of 4-difluoromethoxy-indan-1-one

10.0 g (76.5 mmol) 4-hydroxy-indan-1-one was added to a suspension of 28.0 g (202 mmol) K₂CO₃ in 100 ml dry DMF and stirred overnight at 20° C. The suspension was heated to 85° C. and treated with 17.0 g (202 mmol) gaseous CHClF2 for 45 minutes while maintaining the temperature at 85° C. The resulting dark suspension was cooled to room temperature and poured into 1500 ml water. The mixture was extracted with EtOAc. After separation the organic layer was washed with water and brine, dried over MgSO₄ and evaporated to dryness. The crude product was purified by flash chromatography (hexane/EtOAc 9:1) to give 7.0 g (52%) of 4-difluoro-methoxy-indan-1-one with mp 61-67° C.

1H-NMR (ppm, CDCl₃): 2.70-2.75 (m, 2H), 3.15-3.2 (m, 2H), 6.65 (t, broad, 1H) 7.35-7.45 (m, 2H), 7.65 (d, 1H).

INTERMEDIATE EXAMPLE 4

This Example illustrates the preparation of 2-p-tolyloxy-thiazoline

(according to Iwakura at al. J. Org. Chem. 1967, 32, 2362) Solid 2-aminoethylbromide hydrobromide (6.57 g, 32.1 mmol) was added to a solution of para tolylchlorothionoformate (5 ml, 6.05 g, 32.1 mmol) in tBuOMe (50 ml) with stirring at 0° C. NaOH (2M, 35 ml) was slowly added causing an exotherm to 29° C. After stirring at 0° C. for ca 30 minutes, NaOH (8M, ca 30 ml) was added to make the mixture basic. The product was extracted into tBuOMe, washed with NaHCO₃ (1M) and NaCl (sat.), dried (MgSO₄) and evaporated to yield 5.125 g (83%) of the product as a colourless oil. ¹H-NMR (300 MHz, CDCl₃): 2.32 (3H, s, Me); 3.51 (2H, t, J=8); 4.06 (2H, t, J=8); 7.09 (2H, d, J=8); 7.18 (2H, d, J=8).

EXAMPLE 12

This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I).

Test against were performed as follows:

Heliothis virescens (Tobacco Budworm):

Eggs (0-24 h old) were placed in 24-well microtiter plate on artificial diet and treated with test solutions at an application rate of 200 ppm by pipetting. After an incubation period of 4 days, samples were checked for egg mortality, larval mortality, and growth regulation. The following compounds gave at least 80% control of Heliothis virescens: 2.025, 2.024, 2.022, 2.001, 2.020, 2.031, 2.003, 2.019, 2.026, 7.010, 2.030, 2.032, 1.007, 2.028, 2.040, 2.048, 2.049, 2.052, 2.058, 2.067, 6.022, 6.023, 6.026, 6.027, 6.032, 6.035, 6.038, 8.017, 8.018, 8.025, 8.031, 8.033, 8.034, 9.018, 9.019, 9.020, 10.001, 10.009, 10.011, 10.013, 10.015, 10.017, 10.020, 10.022, 10.025, 12.008, 12.012, 12.017.

Myzus persicae (Green Peach Aphid):

Sunflower leaf discs were placed on agar in a 24-well microtiter plate and sprayed with test solutions at an application rate of 200/50/12.5 ppm. After drying, the leaf discs were infested with an aphid population of mixed ages. After an incubation period of 6 DAT, samples were checked for mortality.

The following compounds gave at least 80% control of Myzus persicae: 2.025, 2.024, 2.022, 2.001, 7.006, 2.020, 2.031, 6.019, 4.001, 2.002, 2.003, 2.006, 2.019, 2.016, 7.007, 2.026, 7.008, 2.014, 7.010, 2.030, 1.012, 2.014, 2.031, 2.032, 2.052, 2.058, 2.066, 6.020, 6.022, 6.032, 6.042, 8.017, 8.018, 8.030, 8.031, 8.032, 8.036, 9.001, 9.020, 10.002, 10.012, 10.013, 10.014, 10.015, 10.019, 10.020, 10.021, 10.022, 10.025, 12.008, 12.010, 12.011.

Myzus persicae (Green Peach Aphid):

Roots of pea seedlings, infested with an aphid population of mixed ages, were placed directly in the test solutions of 24 ppm. 6 days after introduction, samples were checked for mortality.

The following compounds gave at least 80% control of Myzus persicae: 2.025, 2.024, 2.022, 2.001, 2.031, 4.001, 2.003, 2.006, 2.019, 2.030, 2.058, 2.066, 2.067, 7.006, 8.025, 10.002, 10.006, 10.009, 10.011, 10.015.

Tetranychus urticae (Two-Spotted Spider Mite):

Bean leaf discs on agar in 24-well microtiter plates were sprayed with test solutions at an application rate of 200/50/12.5 ppm. After drying, the leaf discs are infested with mite populations of mixed ages. 8 days later, discs are checked for egg mortality, larval mortality, and adult mortality.

The following compounds gave at least 80% control of Tetranychus urticae: 2.024, 2.022, 7.006, 2.020, 2.006, 2.019, 7.010, 2.030, 2.058, 2.066, 2.067, 6.022, 6.032, 7.006, 8.018, 8.025, 8.026, 8.027, 8.031, 8.032. 

1. A compound of formula IC

wherein X is (i), (ii) or (iii)

Y is O, S(O)_(m), NR³ or CR⁵R⁶; m is 0, 1, or 2; the ring (T)

is a 5- or 6-membered aromatic or heteroaromatic ring; R¹, R², R⁵ and R⁶ are each independently H, OH, halogen, nitro, cyano, rhodano, carboxy, formyl, formyloxy, G-, G-O—, G-S—, G-A-, R²¹R²²N—, R²¹R²²N-A-, G-O-A-, G-S-A-, G-A-O—, G-A-S—, G-A-NR²³—, R²¹R²²N-A-O—, R²¹R²²N-A-S—, R²¹R²²N-A-NR²³—, G-O-A-O—, G-O-A-S—, G-O-A-NR²³—, G-S-A-O, G-S-A-NR²³—, or R²⁰S(O)(═NR¹⁷)—, or two of the groups R¹, R², R⁵ and R⁶ attached to the same carbon atom are ═O, ═S, ═NR¹¹ or ═CR¹²R¹³, or the groups R¹ and R² or R⁵ and R⁶ together with the carbon atom to which they are attached form a three to six membered ring containing at least 2 carbon atoms and optionally containing (i) one or two sulfur atoms, (ii) one or two non-adjacent oxygen atoms, (iii) or a combination of (i) and (ii), or a group NR¹⁴, the ring being optionally substituted by C₁-C₆ alkyl; or two of the groups R¹, R², R⁵ and R⁶ attached to different atoms together with the atoms they are attached form a three to seven membered ring that optionally contains (i) one or two sulfur atoms, (ii) one or two non-adjacent oxygen atoms, (iii) or a combination of (i) and (ii), or a group NR¹⁴, the ring being optionally substituted by C₁-C₆ alkyl or two of the groups R¹, R², R⁵ and R⁶ attached to adjacent atoms combine to form a bond; R¹⁰ is H, OH, cyano, formyl, tri(C₁-C₆ alkyl)silyl, G-, G-O—, G-S—, G-S—S—, G-A-, R²⁴R²⁵N—, R²⁴R²⁵N—S—, R²⁴R²⁵N-A-, R¹⁸N═C(R¹⁹)—, G-A-NR⁶⁹—, R⁷⁰R⁷¹C═N, G-O-A- or G-S-A-, R¹¹ is H, OH, nitro, cyano, formyl, formyloxy, G-, G-O—, G-A-, R³⁶R³⁷N—, G-C(O)—O—, G-C(O)—NR²⁶—, R³⁶R³⁷N—C(O)—, G-OC(O)O—, or G-OC(O)—NR²⁶—; R¹² and R¹³ are each independently H, halogen, nitro, cyano, formyl, formyloxy, G-, G-O—, G-S—, G-A-, R⁴⁰R⁴¹N—, R⁴⁰R⁴¹N-A-, G-O-A-, G-A-O—, R⁴⁰R⁴¹N-A-O—, R⁴⁰R⁴¹N-A-S—, G-O-A-O—, G-O-A-S—, or G-O-A-NR³⁰—, or R¹² and R¹³ together with the carbon atom to which they are attached form a 3 to 6 membered carbocyclic ring; R³, R¹⁴, R¹⁵ and R¹⁶ are each independently H, OH, cyano, formyl, G-, G-O—, G-S—, G-A-, R²⁷R²⁸N—, R²⁷R²⁸N-A-, G-O-A-, G-S-A-, G-A-NR²⁹—, R²⁷R²⁸N-A-NR²⁹—, G-O-A-NR²⁹— or G-S-A-NR²⁹—; each R⁴ is independently OH, halogen, nitro, cyano, azido, rhodano, isothiocyanato, carboxy, formyl, formyloxy, G-, G-O—, G-S—, G-A-, R³¹R³²N—, R³¹R³²N-A-, G-O-A-, G-S-A-, G-A-O—, G-A-S—, G-A-NR³³—, R³¹R³²N-A-O—, R³¹R³²N-A-S—, R³¹R³²N-A-NR³³⁻⁵ G-O-A-O—, G-O-A-S—, G-O-A-NR³³—, G-S-A-O, G-S-A-NR³³—, R²⁰S(O)(═NR¹⁷)—, R¹⁸N═C(R¹⁹)—, R⁴⁴R⁴⁵P(O)— or R⁴⁴R⁴⁵P(S)—, or 2 adjacent groups R⁴ together with the carbon atoms to which they are attached form a 4, 5, 6, or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen, or a group R⁴ together with a group R³, R⁵ or R⁹ and the atoms to which they are attached form a 5-7 membered ring optionally containing an NR¹⁵ group or an S or O atom, the ring being optionally substituted by C₁-C₆ alkyl; n is 0, 1, 2, 3 or 4; R⁹ is H, formyl, G, G-A-, R³⁴R³⁵N-A-, G-O-A- or G-S-A-, or R⁹ together with a group R¹ or R⁵ and the atoms to which they are attached may form a three to seven membered ring that optionally may contain (i) one or two sulfur atoms, (ii) one or two non-adjacent oxygen atoms, (iii) or a combination of (i) and (ii), or a group NR¹⁶; R¹⁷ is H, G-, G-C(O)— or G-OC(O)—; R¹⁸ is H, OH, cyano, nitro, G-, G-O— or R³⁸R³⁹N—; R¹⁹ is H, cyano, G-, G-O—, G-S— or R⁴²R⁴³N—; R²⁰ is C₁₋₆ alkyl, optionally substituted phenyl, or optionally substituted benzyl; each of the groups R²¹ to R⁴³ inclusive are independently H or G-, or two R²¹, R²², R²⁷, R²⁸, R³¹, R³², R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴² or R⁴³ groups, together with the N atom to which they are attached, form a group N═CR^(a)R^(b) where R^(a) and R^(b) are each independently H or C₁₋₆-alkyl, R²¹, R²², R²⁴, R²⁵, R²⁷, R²⁸, R³¹, R³², R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹, R⁴² or R⁴³ groups, together with the N atom to which they are attached, form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one to four C₁₋₆ alkyl groups; R⁴⁴ and R⁴⁵ are each independently C₁₋₆alkyl, C₁₋₆-alkoxy, phenyl, or phenoxy; G is optionally substituted C₁₋₁₂ alkyl, optionally substituted C₂₋₁₂ alkenyl, optionally substituted C₂₋₁₂ alkynyl, optionally substituted C₃₋₈ cycloalkyl, optionally substituted C₃₋₈ cycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl; R⁶⁹ is H, G-, G-C(O)— or G-OC(O)—; R⁷⁰ and R⁷¹ are each independently H, cyano, nitro, G-, G-O—, or G-S—, or R⁷⁰ and R⁷¹ together with the carbon atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one to four C₁₋₆ alkyl groups; A is S(O), SO₂, C(O) or C(S); or salts or N-oxides thereof, provided that any compound having formulae (IC1) to (IC3) is excluded:

wherein R¹⁰⁰ is hydrogen or acetyl, and

wherein R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ are hydrogen, R²⁰⁰ and R³⁰⁰ are independently of each other halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ alkylthio, trifluoromethyl or trifluoromethoxy, s and t are independently of each other 0, 1, 2 or 3, and the total of s+t is not greater than
 3. 2. Compounds according to claim 1 of the formula ID

or salts or N-oxides thereof, wherein Y is CR⁵R⁶, and at least one of R¹, R², R⁴, R⁵, R⁶ or R⁹ is fluorine.
 3. Compounds according to claim 1 of formula IE

or salts or N-oxides thereof, wherein Y is CR⁵R⁶, and n is 0, 1, 2 or
 3. 4. Compounds according to claim 1, wherein Y is CR⁵R⁶.
 5. Compounds according to claim 1, wherein the ring (T) is a 6-membered aromatic ring.
 6. Compounds according to claim 1, wherein X is (ii).
 7. Compounds according to claim 6, wherein R¹⁰ is cyano.
 8. Compounds according to claim 4, wherein the ring (T) is a 6-membered aromatic ring.
 9. Compounds according to claim 8, wherein X is (ii).
 10. Compounds according to claim 9, wherein R¹⁰ is cyano.
 11. Compounds according to claim 10, wherein n is
 0. 12. Compounds according to claim 11, wherein R¹, R², R⁵, R⁶, and R⁹ are H.
 13. Compounds according to claim 5, wherein n is
 0. 14. Compounds according to claim 5, wherein X is (ii).
 15. Compounds according to claim 14, wherein R¹⁰ is cyano.
 16. Compounds according to claim 14, wherein n is
 0. 